Stabilizer mixtures

ABSTRACT

A stabilizer mixture containing 
     (I) two different sterically hindered amine compounds, and 
     (II) at least one compound selected from the group consisting of an organic salt of Zn, an inorganic salt of Zn, Zn oxide, Zn hydroxide, an organic salt of Mg, an inorganic salt of Mg, Mg oxide and Mg hydroxide.

The present invention relates to a stabilizer mixture containing twodifferent sterically hindered amine compounds and at least one Mg-and/or Zn-compound, the use of this mixture for stabilizing an organicmaterial, in particular a polyolefin, against degradation induced bylight, heat or oxidation and the organic material thus stabilized. Thestabilization of polyolefins is described in numerous publications, forexample in U.S. Pat. Nos. 4,929,652, 5,025,051, 5,037,870, EP-A-276,923,EP-A-290,388, EP-A-429,731, EP-A-468,923, EP-A-661,341, EP-A-690,094,DE-A-19,545,896 (Derwent 96-278,994/29; Chemical Abstracts 125:116779q),WO-A-95/25,767, GB-A-2,293,827, Chemical Abstracts 106:197407z,GB-A-2,332,678, WO-A-00/11,065, GB-A-2,316,409, GB-A-2, 332,677,Chemical Abstracts 132: 335,575t and Research Disclosure 34,549.

In more detail, the present invention relates to

a stabilizer mixture containing

(I) two different sterically hindered amine compounds, and

(II) at least one compound selected from the group consisting of anorganic salt of Zn, an inorganic salt of Zn, Zn oxide, Zn hydroxide, anorganic salt of Mg, an inorganic salt of Mg, Mg oxide and Mg hydroxide;

with the proviso that component (I) is different from the combination ofthe compounds (B-8-a) and (B-8-b):

wherein n₂ and n₂* are a number from 2 to 50; and

with the proviso that, when

component (I) is the combination of the compounds (B-1-a-1) and (B-7-a):

wherein b₁ is a number from 2 to 50,

wherein n₁ is a number from 2 to 50; and,

at the same time, component (II) is a Zn carboxylate;

the stabilizer mixture additionally contains as a further component

(X-1) a pigment or

(X-2) an UV absorber or

(X-3) a pigment and an UV absorber.

A preferred embodiment of the present invention relates to a stabilizermixture containing as component (I) two different sterically hinderedamine compounds wherein one sterically hindered amine compound is acompound of the formula (B-1-b) or (B-1-d):

wherein b₁ is a number from 2 to 20 and R₆ is hydrogen, C₁-C₈alkyl, O⁻,—OH, —CH₂CN, C₁-C₁₈alkoxy, C₅-C₁₂cycloalkoxy, C₃-C₆alkenyl,C₇-C₉phenylalkyl unsubstituted or substituted on the phenyl by 1, 2 or 3C₁-C₄alkyl; or C₁-C₈acyl; and

the other sterically hindered amine compound is a compound of theformula (B-7-a)

wherein n₁ is a number from 2 to 20; and

component (II) is an organic salt of Zn, an inorganic salt of Zn, Znoxide or Zn hydroxide; preferably Zn carboxylate.

Preferably, a stabilizer mixture containing a compound of the class(β-1) as defined below, a compound of the class (β-7) as defined belowand Zn-carboxylate, in particular an organic salt of Zn, is disclaimed.

According to a preferred embodiment of the present invention, component(II) is an organic salt of Mg, an inorganic salt of Mg, Mg oxide or Mghydroxide, when component (I) is the combination of a compound of theclass (β-1) as defined below, and a compound of the class (β-7) asdefined below.

The stabilizer mixtures according to the present invention preferably donot contain a mineral oil.

The two different sterically hindered amine compounds of component (I)are preferably selected from the group consisting of the followingclasses

(α-1) a compound of the formula (A-1):

in which

E₁ is hydrogen, C₁-C₈alkyl, O⁻, —OH, —CH₂CN, C₁-C₁₈alkoxy,C₅-C₁₂cycloalkoxy, C₃-C₆alkenyl, C₇-C₉phenylalkyl unsubstituted orsubstituted on the phenyl by 1, 2 or 3 C₁-C₄alkyl; or

C₁-C₈acyl,

m₁ is 1, 2 or 4,

if m₁ is 1, E₂ is C₁-C₂₅alkyl,

if m₁ is 2, E₂ is C₁C₁₄alkylene or a group of the formula (a-I):

wherein E₃ is C₁-C₁₀alkyl or C₂-C₁₀alkenyl, E₄ is C₁-C₁₀alkylene, and

E₅ and E₆ independently of one another are C₁-C₄alkyl, cyclohexyl ormethylcyclohexyl, and

if m₁ is 4, E₂ is C₄-C₁₀alkanetetrayl;

(α-2) a compound of the formula (A-2):

in which

two of the radicals E₇ are —COO—(C₁-C₂₀alkyl), and

two of the radicals E₇ are a group of the formula (a-II):

with E₈ having one of the meanings of E₁;

(α-3) a compound of the formula (A-3):

in which

E₉ and E₁₀ together form C₂-C₁₄alkylene,

E₁₁ is hydrogen or a group —Z₁—COO—Z₂,

Z₁ is C₂-C₁₄alkylene, and

Z₂ is C₁-C₂₄alkyl, and

E₁₂ has one of the meanings of E₁;

(α-4) a compound of the formula (A-4):

wherein

the radicals E₁₃ independently of one another have one of the meaningsof E₁,

the radicals E₁₄ independently of one another are hydrogen orC₁-C₁₂alkyl, and

E₁₅ is C₁-C₁₀alkylene or C₃-C₁₀alkylidene;

(α-5) a compound of the formula (A-5):

wherein

the radicals E₁₆ independently of one another have one of the meaningsof E₁;

(α-6) a compound of the formula (A-6):

in which

E₁₇ is C₁-C₂₄alkyl, and

E₁₈ has one of the meanings of E₁;

(α-7) a compound of the formula (A-7):

in which

E₁₉, E₂₀ and E₂₁ independently of one another are a group of the formula(a-IlI):

wherein E₂₂ has one of the meanings of E₁;

(α-8) a compound of the formula (A-8):

wherein

the radicals E₂₃ independently of one another have one of the meaningsof E₁,

and E₂₄ is hydrogen, C₁-C₁₂alkyl or C₁-C₁₂alkoxy;

(α-9) a compound of the formula (A-9):

wherein

m₂ is 1, 2 or 3,

E₂₅ has one of the meanings of E₁, and

when m₂ is 1, E₂₆ is a group

when m₂ is 2, E₂₆ is C₂-C₂₂alkylene, and

when m₂ is 3, E₂₆ is a group of the formula (a-IV):

wherein the radicals E₂₇ independently of one another areC₂-C₁₂alkylene, and

the radicals E₂₈ independently of one another are C₁-C₁₂alkyl orC₅-C₁₂cycloalkyl;

(α-10) a compound of the formula (A-10):

wherein

the radicals E₂₉ independently of one another have one of the meaningsof E₁, and

E₃₀ is C₂-C₂₂alkylene, C₅-C₇cycloalkylene,C₁-C₄alkylenedi(C₅-C₇cycloalkylene), phenylene orphenylenedi(C₁-C₄alkylene);

(β-1) a compound of the formula (B-1):

in which

R₁, R₃, R₄ and R₅ independently of one another are hydrogen,C₁-C₁₂alkyl, C₅-C₁₂cycloalkyl, C₁-C₄-alkyl-substituted C₅-C₁₂cycloalkyl,phenyl, phenyl which is substituted by —OH and/or C₁-C₁₀alkyl;C₇-C₉phenylalkyl, C₇-C₉phenylalkyl which is substituted on the phenylradical by —OH and/or C₁-C₁₀alkyl; or a group of the formula (b-I):

R₂ is C₂-C₁₈alkylene, C₅-C₇cycloalkylene orC₁-C₄alkylenedi(B₅—C₇cycloalkylene), or

the radicals R₁, R₂ and R₃, together with the nitrogen atoms to whichthey are bonded, perform a 5- to 10-membered heterocyclic ring, or

R₄ and R₅, together with the nitrogen atom to which they are bonded,form a 5- to 10-membered heterocyclic ring,

R₆ is hydrogen, C₁-C₈alkyl, O⁻, —OH, —CH₂CN, C₁-C₁₈alkoxy,C₅-C₁₂cycloalkoxy, C₃-C₆alkenyl,

C₇-C₉phenylalkyl unsubstituted or substituted on the phenyl by 1, 2 or 3C₁-C₄alkyl; or

C₁-C₈acyl, and

b₁ is a number from 2 to 50,

with the proviso that at least one of the radicals R₁, R₃, R₄ and R₅ isa group of the formula (b-I);

(β-2) a compound of the formula (B-2):

wherein

R₇ and R₁₁ independently of one another are hydrogen or C₁-C₁₂alkyl,

R₈, R₉ and R₁₀ independently of one another are C₂-C₁₀alkylene, and

X₁, X₂, X₃, X₄, X₅, X₆, X₇ and X₈ independently of one another are agroup of the formula (b-II):

in which R₁₂ is hydrogen, C₁-C₁₂alkyl, C₅-C₁₂cycloalkyl,C₁-C₄alkyl-substituted C₅-C₁₂cycloalkyl, phenyl, —OH— and/orC₁-C₁₀alkyl-substituted phenyl, C₇-C₉phenylalkyl, C₇-C₉phenylalkyl whichis substituted on the phenyl radical by —OH and/or C₁-C₁₀alkyl; or agroup of the formula (b-I) as defined above, and

R₁₃ has one of the meanings of R₆;

(β-3) a compound of the formula (B-3):

in which

R₁₄ is C₁-C₁₀alkyl, C₅-C₁₂cycloalkyl, C₁-C₄alkyl-substitutedC₅-C₁₂cycloalkyl, phenyl or

C₁-C₁₀alkyl-substituted phenyl,

R₁₅ is C₃-C₁₀alkylene,

R₁₆ has one of the meanings of R₆, and

b₂ is a number from 2 to 50;

(β-4) a compound of the formula (B-4):

in which

R₁₇ and R₂₁ independently of one another are a direct bond or a—N(X₉)—CO—X₁₀—CO—N(X₁₁)-group, where X₉ and X₁₁ independently of oneanother are hydrogen, C₁-C₈alkyl, C₅-C₁₂cycloalkyl, phenyl,C₇-C₉phenylalkyl or a group of the formula (b-I),

X₁₀ is a direct bond or C₁-C₄alkylene,

R₁₈ has one of the meanings of R₆,

R₁₉, R₂₀, R₂₃ and R₂₄ independently of one another are hydrogen,C₁-C₃₀alkyl,

C₅-C₁₂cycloalkyl or phenyl,

R₂₂ is hydrogen, C₁-C₃₀alkyl, C₅-C₁₂cycloalkyl, phenyl, C₇-C₉phenylalkylor a group of the formula (b-I), and

b₃ is a number from 1 to 50;

(β-5) a compound of the formula (B-5):

in which

R₂₅, R₂₆, R₂₇, R₂₈ and R₂₉ independently of one another are a directbond or C₁-C₁₀alkylene,

R₃₀ has one of the meanings of R₆, and

b₄ is a number from 1 to 50;

(β-6) a product (B-6) obtainable by reacting a product, obtained byreaction of a polyamine of the formula (B-6-1) with cyanuric chloride,with a compound of the formula (B-6-2):

H₂N—(CH₂)_(b) ₅ _(′)—NH—(CH₂)_(b) ₅ _(″)—NH—(CH₂)_(b) ₅_(′″)—NH₂  (B-6-1)

in which

b₅′, b₅″ and b₅′″ independently of one another are a number from 2 to12,

R₃₁ is hydrogen, C₁-C₁₂alkyl, C₅-C₁₂cycloalkyl, phenyl orC₇-C₉phenylalkyl, and

R₃₂ has one of the meanings of R₆;

(β-7) a compound of the formula (B-7):

wherein A₁ is hydrogen or C₁-C₄alkyl,

A₂ is a direct bond or C₁-C₁₀alkylene, and

n₁ is a number from 2 to 50;

(β-8) at least one compound of the formulae (B-8-a) and (B-8-b):

wherein n₂ and n₂* are a number from 2 to 50;

(β-9) a compound of the formula (B-9):

wherein A₃ and A₄ independently of one another are hydrogen orC₁-C₈alkyl, or A₃ and A₄ together form a C₂-C₁₄alkylene group, and

the variables n₃ independently of one another are a number from 1 to 50;and

(β-10) a compound of the formula (B-10):

wherein n₄ is a number from 2 to 50,

A₅ is hydrogen or C₁-C₄alkyl,

the radicals A₆ and A₇ independently of one another are C₁-C₄alkyl or agroup of the formula (b-I),

with the proviso that at least 50% of the radicals A₇ are a group of theformula (b-I).

Examples of component (I) are:

A compound selected from the class α-1 and a compound selected from theclass α-3, α-5, α-6, α-7, α-9, α-10, β-1, β-2, β-3, β-4, β-5, β-6, β-7,β-8 or β-9.

A compound selected from the class α-3 and a compound selected from theclass α-5, α-6, α-7, α-9, α-10, β-1, β-2, β-3, β-4, β-5, β-6, β-7, β-8or β-9.

A compound selected from the class α-5 and a compound selected from theclass α-6, α-7, α-9, α-10, β-1, β-2, β-3, β-4, β-5, β-6, β-7, β-8 orβ-9.

A compound selected from the class α-6 and a compound selected from theclass α-9, α-10, β-1, β-2, β-3, β-4, β-5, β-6, β-7, β-8 or β-9.

A compound selected from the class α-7 and a compound selected from theclass α-9, α-10, β-1, β-2, β-3, β-4, β-5, β-6, β-7, β-8 or β-9.

A compound selected from the class α-10 and a compound selected from theclass β-1, β-2, β-3, β-4β-5, β-6, β-7, β-8 or β-9.

A compound selected from the class β-1 and a compound selected from theclass β-2, β-3, β-4, β-5, β-6, β-7, β-8, β-9 or β-10.

A compound selected from the class β-2 and a compound selected from theclass β-3, β-4, β-5, β-6, β-7, β-8, β-9 or β-10.

A compound selected from the class β-3 and a compound selected from theclass β-4, β-5, β-6, β-7, β-8, β-9 or β-10.

A compound selected from the class β-4 and a compound selected from theclass β-5, β-6, β-7, β-8, β-9 or β-10.

A compound selected from the class β-5 and a compound selected from theclass β-6, β-7, β-8, β-9 or β-10.

A compound selected from the class β-6 and a compound selected from theclass β-7, β-8, β-9 or β-10.

A compound selected from the class β-7 and a compound selected from theclass β-8, β-9 or β-10.

A compound selected from the class β-8 and a compound selected from theclass β-9 or β-10.

A compound selected from the class β-9 and a compound selected from theclass β-10.

According to a preferred embodiment,

the two different sterically hindered amine compounds of component (I)are selected from the group consisting of the classes (α-1), (α-2),(α-3), (α-4), (α-5), (α-6), (α-7), (α-8), (α-9) and (α-10).

According to a further preferred embodiment,

the two different sterically hindered amine compounds of component (I)are selected from the group consisting of the classes (β-1), (β-2),(β-3), (β-4), (β-5), (β-6), (β-7), (β-8), (β-9) and (β-10).

According to another preferred embodiment,

one of the two different sterically hindered amine compounds ofcomponent (I) is selected from the group consisting of the classes(α-1), (α-2), (α-3), (α-4), (α-5), (α-6), (β-7), (β-8), (α-9) and(α-10), and

the other of the two different sterically hindered amine compounds ofcomponent (I) is selected from the group consisting of the classes(β-1), (β-2), (β-3), (β-4), (β-5), (β-6), (β-7), (β-8), (β-9) and(β-10).

One of the two different sterically hindered amine compounds ofcomponent (I) is preferably selected from the class (β-1).

According to a particularly preferred embodiment,

one of the two different sterically hindered amine compounds ofcomponent (I) is selected from the class (β-1), and

the other of the two different sterically hindered amine compounds ofcomponent (I) is selected from the class (α-1) or (β-7).

According to another particularly preferred embodiment,

one of the two different sterically hindered amine compounds ofcomponent (I) is selected from the class (β-7), and

the other of the two different sterically hindered amine compounds ofcomponent (I) is selected from the class (β-2).

The two different sterically hindered amine compounds of component (I)are preferably selected from different classes.

Examples of alkyl having up to 30 carbon atoms are methyl, ethyl,propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl,2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1,3-dimethyl-butyl,n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl,1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl,1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl,1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl, tridecyl,tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl,docosyl and triacontyl. One of the preferred definitions of E₁, E₈, E₁₂,E₁₃, E₁₆, E₁₈, E₂₂, E₂₃, E₂₅, E₂₉, R₆, R₁₃, R₁₆, R₁₈, R₃₀ and R₃₂ isC₁-C₄alkyl, especially methyl. R₃₁ is preferably butyl.

Examples of alkoxy having up to 18 carbon atoms are methoxy, ethoxy,propoxy, isopropoxy, butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy,heptoxy, octoxy, decyloxy, dodecyloxy, tetradecyloxy, hexadecyloxy andoctadecyloxy. One of the preferred meanings of E₁ is octoxy. E₂₄ ispreferably C₁-C₄alkoxy and one of the preferred meanings of R₆ ispropoxy.

Examples of C₅-C₁₂cycloalkyl are cyclopentyl, cyclohexyl, cycloheptyl,cyclooctyl and cyclododecyl. C₅-C₈Cycloalkyl, especially cyclohexyl, ispreferred.

C₁-C₄Alkyl-substituted C₅-C₁₂cycloalkyl is for example methylcyclohexylor dimethylcyclohexyl.

Examples of C₅-C₁₂cycloalkoxy are cyclopentoxy, cyclohexoxy,cycloheptoxy, cyclooctoxy, cyclodecyloxy and cyclododecyloxy.C₅-C₈Cycloalkoxy, in particular cyclopentoxy and cyclohexoxy, ispreferred.

—OH— and/or C₁-C₁₀alkyl-substituted phenyl is for example methylphenyl,dimethylphenyl, trimethylphenyl, tert-butylphenyl or3,5-di-tert-butyl-4-hydroxyphenyl.

Examples of C₇-C₉phenylalkyl are benzyl and phenylethyl.

C₇-C₉Phenylalkyl which is substituted on the phenyl radical by —OHand/or by alkyl having up to 10 carbon atoms is for examplemethylbenzyl, dimethylbenzyl, trimethylbenzyl, tert-butylbenzyl or3,5-di-tert-butyl-4-hydroxybenzyl.

Examples of alkenyl having up to 10 carbon atoms are allyl, 2-methallyl,butenyl, pentenyl and hexenyl. Allyl is preferred. The carbon atom inposition 1 is preferably saturated.

Examples of acyl containing not more than 8 carbon atoms are formyl,acetyl, propionyl, butyryl, pentanoyl, hexanoyl, heptanoyl, octanoyl,acryloyl, methacryloyl and benzoyl. C₁-C₈Alkanoyl, C₃-C₈alkenyl andbenzoyl are preferred. Acetyl and acryloyl are especially preferred.

Examples of alkylene having up to 22 carbon atoms are methylene,ethylene, propylene, trimethylene, tetramethylene, pentamethylene,2,2-dimethyltrimethylene, hexamethylene, trimethylhexamethylene,octamethylene and decamethylene.

An example of C₃-C₁₀alkylidene is the group

An example of C₄-C₁₀alkanetetrayl is 1,2,3,4-butanetetrayl.

An example of C₅-C₇cycloalkylene is cyclohexylene.

An example of C₁-C₄alkylenedi(C₅-C₇cycloalkylene) ismethylenedicyclohexylene.

An example of phenylenedi(C₁-C₄alkylene) ismethylene-phenylene-methylene or ethylene-phenylene-ethylene.

Where the radicals R₁, R₂ and R₃, together with the nitrogen atoms towhich they are attached, form a 5- to 10-membered heterocyclic ring,this ring is for example:

A 6-membered heterocyclic ring is preferred.

Where the radicals R₄ and R₅, together with the nitrogen atom to whichthey are attached, form a 5- to 10-membered heterocyclic ring, this ringis for example 1-pyrrolidyl, piperidino, morpholino, 1-piperazinyl,4-methyl-1-piperazinyl, 1-hexahydroazepinyl,5,5,7-trimethyl-1-homopiperazinyl or4,5,5,7-tetramethyl-1-homopiperazinyl. Morpholino is particularlypreferred.

One of the preferred definitions of R₁₉ and R₂₃ is phenyl.

R₂₆ is preferably a direct bond.

n₁, n₂, n₂* and n₄ are preferably a number from 2 to 25, in particular 2to 20. n₃ is preferably a number from 1 to 25, in particular 1 to 20.

b₁ and b₂ are preferably a number from 2 to 25, in particular 2 to 20.

b₃ and b₄ are preferably a number from 1 to 25, in particluar 1 to 20.

b₅′ and b₅′″ are preferably 3 and b₅″ is preferably 2.

The compounds described above as components (I) and (II) are essentiallyknown and commercially available. All of them can be prepared by knownprocesses.

The preparation of the compounds of component (I) is disclosed, forexample, in U.S. Pat. Nos. 5,679,733, 3,640,928, 4,198,334, 5,204,473,4,619,958, 4,110,306, 4,110,334, 4,689,416, 4,408,051, SU-A-768,175(Derwent 88-138,751/20), U.S. Pat. Nos. 5,049,604, 4,769,457, 4,356,307,4,619,956, 5,182,390, GB-A-2,269,819, U.S. Pat. Nos. 4,292,240,5,026,849, 5,071,981, 4,547,538, 4,976,889, 4,086,204, 6,046,304,4,331,586, 4,108,829, 5,051,458, WO-A-94/12,544 (Derwent 94-177,274/22),DD-A-262,439 (Derwent 89-122,983/17), U.S. Pat. Nos. 4,857,595,4,529,760, 4,477,615, CAS 136,504-96-6, U.S. Pat. Nos. 4,233,412,4,340,534, WO-A-98/51,690 and EP-A-1,803.

The product (B-6) can be prepared analogously to known processes, forexample by reacting a polyamine of formula (B-6-1) with cyanuricchloride in a molar ratio of from 1:2 to 1:4 in the presence ofanhydrous lithium carbonate, sodium carbonate or potassium carbonate inan organic solvent such as 1,2-dichloroethane, toluene, xylene, benzene,dioxane or tert-amyl alcohol temperature of from −20° C. to +10° C.,preferably from −10° C. to +10° C., in particular from 0° C. to +10° C.,for from 2 to 8 hours, followed by reaction of the resultant productwith a 2,2,6,6-tetramethyl-4-piperidylamine of the formula (B-6-2). Themolar ratio of the 2,2,6,6-tetramethyl-4-piperidylamine to polyamine ofthe formula (B-6-1) employed is for example from 4:1 to 8:1. Thequantity of the 2,2,6,6-tetramethyl-4-piperidylamine can be added in oneportion or in more than one portion at intervals of a few hours.

The molar ratio of polyamine of the formula (B-6-1) to cyanuric chlorideto 2,2,6,6-tetramethyl-4-piperidylamine of the formula (B-6-2) ispreferebly from 1:3:5 to 1:3:6.

The following example indicates one way of preparing a preferred product(B-6-a).

EXAMPLE

23.6 g (0.128 mol) of cyanuric chloride, 7.43 g (0.0426 mol) ofN,N′-bis[3-aminopropyl]ethylenediamine and 18 g (0.13 mol) of anhydrouspotassium carbonate are reacted at 5° C. for 3 hours with stirring in250 ml of 1,2-dichloroethane. The mixture is warmed at room temperaturefor a further 4 hours. 27.2 g (0.128 mol) ofN-(2,2,6,6-tetramethyl-4-piperidyl)butylamine are added and theresultant mixture is warmed at 60° C. for 2 hours. A further 18 g (0.13mol) of anhydrous potassium carbonate are added and the mixture iswarmed at 60° C. for a further 6 hours. The solvent is removed bydistillation under a slight vacuum (200 mbar) and replaced by xylene.18.2 g (0.085 mol) of N-(2,2,6,6-tetramethyl-4-piperidyl)butylamine and5.2 g (0.13 mol) of ground sodium hydroxide are added, the mixture isheated at reflux for 2 hours and, for a further 12 hours, the waterformed during the reaction is removed by azeotropic distillation. Themixture is filtered. The solution is washed with water and dried overNa₂SO₄. The solvent is evaporated and the residue is dried at 120-130°C. in vacuo (0.1 mbar). The desired product is obtained as a colourlessresin.

In general, the product (B-6) can, for example, be represented by acompound of the formula (B-6-α), (B-6-β) or (B-6-γ). It can also be inthe form of a mixture of these three compounds:

A preferred meaning of the formula (B-6-α) is:

A preferred meaning of the formula (B-6-β) is:

A preferred meaning of the formula (B-6-γ) is:

In the above formulae (B-6-α) to (B-6-γ), b₅ is preferably 2 to 20, inparticular 2 to 10.

The two different sterically hindered amine compounds of component (I)are preferably selected from the group consisting of the followingcommercial products:

DASTIB 845 (RTM), TINUVIN 770 (RTM), TINUVIN 765 (RTM), TlNUVIN 144(RTM), TINUVIN 123 (RTM), MARK LA 52 (RTM), MARK LA 57 (RTM), MARK LA 62(RTM), MARK LA 67 (RTM), HOSTAVIN N 20 (RTM), HOSTAVIN N 24 (RTM),SANDUVOR 3050 (RTM), DIACETAM 5 (RTM), SUMISORB TM 61 (RTM), UVINUL 4049(RTM), SANDUVOR PR 31 (RTM), GOODRITE UV 3034 (RTM), GOODRITE UV 3150(RTM), GOODRITE UV 3159 (RTM), GOODRITE 3110 x 128 (RTM), UVINUL 4050 H(RTM), CHIMASSORB 944 (RTM), CHIMASSORB 2020 (RTM), CYASORB UV 3346(RTM), CYASORB UV 3529 (RTM), DASTIB 1082 (RTM), CHIMASSORB 119 (RTM),UVASIL 299 (RTM), UVASIL 125 (RTM), UVASIL 2000 (RTM), UVINUL 5050 H(RTM), LICHTSCHUTZSTOFF UV 31 (RTM), LUCHEM HA B 18 (RTM), MARK LA 63(RTM), MARK LA 68 (RTM), UVASORB HA 88 (RTM), TINUVIN 622 (RTM),HOSTAVIN N 30 (RTM) and FERRO AM 806 (RTM).

The meanings of the terminal groups which saturate the free valences inthe compounds of the formulae (B-1), (B-3), (B-4), (B-5), (B-6-α),(B-6-γ), (B-6-γ), (B-7), (B-8-b) and (B-10) depend on the processes usedfor their preparation. The terminal groups can also be modified afterthe preparation of the compounds.

If the compounds of the formula (B-1) are prepared by reacting acompound of the formula:

in which X is, for example, halogen, in particular chlorine, and R₄ andR₅ are as defined above, with a compound of the formula:

in which R₁, R₂ and R₃ are as defined above, the terminal group bondedto the diamino radical is hydrogen or:

and the terminal group bonded to the triazine radical is X or

If X is halogen, it is advantageous to replace this, for example, by —OHor an amino group when the reaction is complete. Examples of aminogroups which may be mentioned are pyrrolidin-1-yl, morpholino, —NH₂,—N(C₁-C₈)alkyl)₂ and —NR(C₁-C₈alkyl), in which R is hydrogen or a groupof the formula (b-I).

The compounds of the formula (B-1) also cover compounds of the formula:

wherein R₁, R₂, R₃, R₄, R₅ and b₁ are as defined above and R₄* has oneof the meanings of R₄ and R₅* has one of the meanings of R₅.

One of the particularly preferred compounds of the formula (B-1) is:

The preparation of this compound is described in Example 10 of U.S. Pat.No. 6,046,304.

In the compounds of the formula (B-3), the terminal group bonded to thesilicon atom can be, for example, (R₁₄)₃Si—O—, and the terminal groupbonded to the oxygen can be, for example, —Si(R₁₄)₃.

The compounds of the formula (B-3) can also be in the form of cycliccompounds if b₂ is a number from 3 to 10, i.e. the free valences shownin the structural formula then form a direct bond.

In the compounds of the formula (B-4), the terminal group bonded to the2,5-dioxopyrrolidine ring is, for example, hydrogen, and the terminalgroup bonded to the —C(R₂₃)(R₂₄)— radical is, for example,

In the compounds of the formula (B-5), the terminal group bonded to thecarbonyl radical is, for example,

and the terminal group bonded to the oxygen radical is, for example,

In the compounds of the formulae (B-6-α), (B-6-β) and (B-6-γ), theterminal group bonded to the triazine radical is, for example, Cl or a

group, and the terminal group bonded to the amino radical is, forexample, hydrogen or a

group.

If the compounds of the formula (B-7) are prepared, for example, byreacting a compound of the formula:

in which A₁ is hydrogen or methyl, with a dicarboxylic acid diester ofthe formula Y—OOC—A₂—COO—Y, in which Y is, for example, methyl, ethyl orpropyl, and A₂ is as defined above, the terminal group bonded to the2,2,6,6-tetramethyl-4-oxypiperidin-1-yl radical is hydrogen or—CO—A₂—COO—Y, and the terminal group bonded to the diacyl radical is—O—Y or

In the compounds of the formula (B-8-a), the terminal group bonded tothe nitrogen can be, for example, hydrogen and the terminal group bondedto the 2-hydroxypropylene radical can be, for example, a

group.

In the compounds of the formula (B-8-b), the terminal group bonded tothe dimethylene radical can be, for example, —OH, and the terminal groupbonded to the oxygen can be, for example, hydrogen. The terminal groupscan also be polyether radicals.

In the compounds of the formula (B-10), the end group bonded to the—CH₂— residue can be, for for example, hydrogen and the end group bondedto the —CH(CO₂A₇) residue can be, example, —CH═CH—COOA₇.

E₁, E₈, E₁₂, E₁₃, E₁₆, E₁₈, E₂₂, E₂₃, E₂₅, E₂₉, R₆, R₁₃, R₁₆, R₁₈, R₃₀and R₃₂ are preferably hydrogen, C₁-C₄alkyl, C₁-C₁₀alkoxy,cyclohexyloxy, allyl, benzyl or acetyl.

E₁, E₈, E₁₂, E₁₃, E₁₆, E₁₈, E₂₂, E₂₃, E₂₅, E₂₉, R₆, R₁₃, R₁₆, R₁₈, R₃₀and R₃₂ are in particular hydrogen or methyl and E₁ and R₆ additionallyare C₁-C₈alkoxy.

According to a preferred embodiment,

m₁ is 1, 2 or 4,

if m₁ is 1, E₂ is C₁₂-C₂₀alkyl,

if m₁ is 2, E₂ is C₂-C₁₀alkylene or a group of the formula (a-I)

E₃ is C₁-C₄alkyl,

E₄ is C₁-C₆alkylene, and

E₅ and E₆ independently of one another are C₁-C₄alkyl, and

if m₁ is 4, E₂ is C₄-C₈alkanetetrayl;

two of the radicals E₇ are —COO—(C₁₀-C₁₅alkyl), and

two of the radicals E₇ are a group of the formula (a-II);

E₉ and E₁₀ together form C₉-C₁₃alkylene,

E₁₁ is hydrogen or a group —Z₁—COO—Z₂,

Z₁ is C₂-C₆alkylene, and

Z₂ is C₁₀-C₁₆alkyl;

E₁₄ is hydrogen, and

E₁₅ is C₂-C₆alkylene or C₃-C₅alkylidene;

E₁₇ is C₁₀-C₁₄alkyl;

E₂₄ is C₁-C₄alkoxy;

m₂ is 1, 2 or 3,

when m₂ is 1, E₂₆ is a group

when m₂ is 2, E₂₆ is C₂-C₆alkylene, and

when m₂ is 3, E₂₆ is a group of the formula (a-IV)

the radicals E₂₇ independently of one another are C₂-C₆alkylene, and

the radicals E₂₈ independently of one another are C₁-C₄alkyl orC₅-C₈cycloalkyl; and

E₃₀ is C₂-C₈alkylene;

R₁ and R₃ independently of one another are a group of the formula (b-I),

R₂ is C₂-C₈alkylene,

R₄ and R₅ independently of one another are hydrogen, C₁-C₁₂alkyl,C₅-C₈cycloalkyl or a group of the formula (b-I), or the radicals R₄ andR₅, together with the nitrogen atom to which they are bonded, form a 5-to 10-membered heterocyclic ring, and b₁ is a number from 2 to 25;

R₇ and R₁₁ independently of one another are hydrogen or C₁-C₄alkyl,

R₈, R₉ and R₁₀ independently of one another are C₂-C₄alkylene, and

X₁, X₂, X₃, X₄, X₅, X₆, X₇ and X₈ independently of one another are agroup of the formula (b-II),

R₁₂ is hydrogen, C₁-C₄alkyl, C₅-C₈cycloalkyl or a group of the formula(b-I);

R₁₄ is C₁-C₄alkyl,

R₁₅ is C₃-C₆alkylene, and

b₂ is a number from 2 to 25;

R₁₇ and R₂₁ independently of one another are a direct bond or a group—N(X₉)—CO—X₁₀—CO—N(X₁₁)—,

X₉ and X₁₁, independently of one another are hydrogen or C₁-C₄alkyl,

X₁₀ is a direct bond,

R₁₉ and R₂₃ are C₁-C₂₅alkyl or phenyl,

R₂₀ and R₂₄ are hydrogen or C₁-C₄alkyl,

R₂₂ is C₁-C₂₅alkyl or a group of the formula (b-I), and

b₃ is a number from 1 to 25;

R₂₅, R₂₆, R₂₇, R₂₈ and R₂₉ independently of one another are a directbond or C₁-C₄alkylene, and

b₄ is a number from 1 to 25;

b₅′, b₅″ and b₅′″ independently of one another are a number from 2 to 4,and

R₃₁ is hydrogen, C₁-C₄alkyl, C₅-C₈cycloalkyl, phenyl or benzyl;

A₁ is hydrogen or methyl,

A₂ is a direct bond or C₂-C₆alkylene, and

n₁ is a number from 2 to 25;

n₂ and n₂* are a number from 2 to 25;

A₃ and A₄ independently of one another are hydrogen or C₁-C₄alkyl, or A₃and A₄ together form a C₉-C₁₃alkylene group, and

the variables n₃ independently of one another are a number from 1 to 25;

n₄ is a number from 2 to 25,

A₅ and A₆ independently of one another are C₁-C₄alkyl, and

A₇ is C₁-C₄alkyl or a group of the formula (b-I) with the proviso thatat least 50% of the radicals A₇ are a group of the formula (b-I).

The two different sterically hindered amine compounds of component (I)are preferably selected from the group consisting of the compounds ofthe formulae (A-1-a), (A-1-b), (A-1-c), (A-1-d), (A-2-a), (A-3-a),(A-3-b), (A-4-a), (A-4-b), (A-5), (A-6-a), (A-7), (A-8-a), (A-9-a),(A-9-b), (A-9-c), (A-10-a), (B-1-a), (B-1-b), (B-1-c), (B-1-d), (B-2-a),(B-3-a), (A-4-a), (B-4-b) and (B-4-c), a product (B-6-a) and thecompounds of the formulae (B-7-a), (B-8-a), (B-8-b), (B-9-a) and(B-10-a);

wherein E₁ is hydrogen, C₁-C₈alkyl, O⁻, —OH, —CH₂CN, C₁-C₁₈alkoxy,C₅-C₁₂cycloalkoxy, C₃-C₆alkenyl, C₇-C₉phenylalkyl unsubstituted orsubstituted on the phenyl by 1, 2 or 3 C₁-C₄alkyl; or C₁-C₈acyl;

in which two of the radicals E₇ are —COO—C₁₃H₂₇ and two of the radicalsE₇ are

and E₈ has one of the meanings of E₁;

wherein E₁₂ has one of the meanings of E₁;

wherein E₁₃ has one of the meanings of E₁;

wherein E₁₆ has one of the meanings of E₁;

wherein E₁₈ has one of the meanings of E₁;

in which E₁₉, E₂₀ and E₂₁ independently of one another are a group ofthe formula (a-III)

wherein E₂₂ has one of the meanings of E₁;

wherein E₂₃ has one of the meanings of E₁;

wherein E₂₅ has one of the meanings of E₁;

wherein E₂₉ has one of the meanings of E₁;

wherein b₁ is a number from 2 to 20 and R₆ is hydrogen, C₁-C₈alkyl, O⁻,—OH, —CH₂CN, C₁-C₁₈alkoxy, C₅-C₁₂cycloalkoxy, C₃-C₆alkenyl,C₇-C₉phenylalkyl unsubstituted or substituted on the phenyl by 1, 2 or 3C₁-C₄alkyl; or C₁-C₈acyl;

wherein R₁₃ has one of the meanings of R₆,

wherein b₂ is a number from 2 to 20 and R₁₆ has one of the meanings ofR₆;

wherein b₃ is a number from 1 to 20 and R₁₈ has one of the meanings ofR₆;

wherein b₄ is a number from 1 to 20 and R₃₀ has one of the meanings ofR₆;

a product (B-6-a) obtainable by reacting a product, obtained by reactionof a polyamine of the formula (B-6-1-a) with cyanuric chloride, with acompound of the formula (B-6-2-a):

in which R₃₂ has one of the meanings of R₆;

wherein n₁ is a number from 2 to 20;

wherein n₂ and n₂* are a number from 2 to 20;

wherein the variables n₃ independently of one another are a number from1 to 20;

wherein n₄ is a number from 2 to 20, and

at least 50% of the radicals A₇ are a group of the formula (b-I):

wherein R₆ is hydrogen, C₁-C₈alkyl, O⁻, —OH, —CH₂CN, C₁-C₁₈alkoxy,C₅-C₁₂cycloalkoxy, C₃-C₆alkenyl, C₇-C₉phenylalkyl unsubstituted orsubstituted on the phenyl by 1, 2 or 3 C₁-C₄alkyl; or C₁-C₈acyl,

and the remaining radicals A₇ are ethyl.

According to a preferred embodiment,

the two different sterically hindered amine compounds of component (I)are

1) a compound of the formula (A-1-b) wherein E₁ is hydrogen, and acompound of the formula (B-1-a) wherein R₆ is hydrogen;

2) a compound of the formula (B-1-a) wherein R₆ is hydrogen, and acompound of the formula (B-7-a); or

3) a compound of the formula (B-2-a) wherein R₁₃ is methyl, and acompound of the formula (B-7-a).

The organic salt of zinc or magnesium defined in component (II) ispreferably a compound of the formula MeL₂ in which Me is zinc ormagnesium and L is an anion of an organic acid or of an enol. Theorganic acid can, for example, be a sulfonic acid, sulfinic acid,phosphonic acid or phosphinic acid, but is preferably a carboxylic acid.The acid can be aliphatic, aromatic, araliphatic or cycloaliphatic; itcan be linear or branched; it can be substituted by hydroxyl or alkoxygroups; it can be saturated or unsaturated and it preferably contains 1to 24 carbon atoms.

Examples of carboxylic acids of this type are formic, acetic, propionic,butyric, isobutyric, caprioic, 2-ethylcaproic, caprylic, capric, lauric,palmitic, stearic, behenic, oleic, lactic, ricinoleic,2-ethoxypropionic, benzoic, salicylic, 4-butylbenzoic, toluic,4-dodecylbenzoic, phenylacetic, naphthylacetic, cyclohexanecarboxylic,4-butylcyclohexanecarboxylic or cyclohexylacetic acid. The carboxylicacid can also be a technical mixture of carboxylic acids, for exampletechnical mixtures of fatty acids or mixtures of alkylated benzoicacids.

Examples of organic acids containing sulfur or phosphorus aremethanesulfonic, ethanesulfonic, α,α-dimethylethanesulfonic,n-butanesulfonic, n-dodecanesulfonic, benzenesulfonic, toluenesulfonic,4-nonylbenzenesulfonic, 4-dodecylbenzenesulfonic or cyclohexanesulfonicacid, dodecanesulfinic, benzenesulfinic or naphthalenesulfinic acid,butylphosphonic acid, phenylphosphonic acid, monomethyl or monoethylphenylphosphonate, monobutyl benzylphosphonate, dibutylphosphinic acidor diphenylphosphinic acid.

If L is an enolate anion, it is preferably an anion of a β-dicarbonylcompound or of an o-acylphenol. Examples of β-dicarbonyl compounds areacetylacetone, benzoylacetone, dibenzoylmethane, ethyl acetoacetate,butyl acetoacetate, lauryl acetoacetate or α-acetylcyclohexanone.Examples of o-acylphenols are 2-acetylphenol, 2-butyroylphenol,2-acetyl-1-naphthol, 2-benzoylphenol or salicylaldehyde. The enolate ispreferably the anion of a β-dicarbonyl compound having 5 to 20 carbonatoms.

Organic salts of zinc or magnesium are preferably an acetylacetonate oran aliphatic monocarboxylate having, for example, 1 to 24 carbon atoms.Magnesium acetate, laurate and stearate, zinc formate, acetate,oenanthate, laurate and stearate as well as zinc acetylacetonate andmagnesium acetylacetonate are some of the particular preferred examples.

Zinc stearate, magnesium stearate, zinc acetylacetonate, magnesiumacetylacetonate, zinc acetate and magnesium acetate are of specialinterest.

The inorganic salt of zinc or magnesium is for example a carbonatecontaining compound such as

Zn-hydroxide-carbonate, Mg-hydroxide-carbonate, dolomite, e.g a Ca/Mgcarbonate such as Microdol Super (RTM) from Micro Minerals (RTM); or

a natural or synthetic hydrotalcite.

The natural hydrotalcite is held to possess a structureMg₆Al₂(OH)₁₆CO₃.4H₂O. A typical empirical formula of a synthetichydrotalcite is

Al₂Mg_(4.35)OH_(11.36)CO_(3(1.67)).xH₂O.

Examples of the synthetic product include:

Mg_(0.7)Al_(0.3)(OH)₂(CO₃)_(0.15).0.54H₂O,

Mg_(4.5)Al₂(OH)₁₃CO₃.3.5H₂O, or

Mg_(4.2)Al(OH)_(12.4)CO₃.

Preferred synthetic hydrotalcites are L-55R II (RTM) from REHEIS (RTM)as well as ZHT-4A (RTM) and DHT-4A (RTM) from Kyowa Chemical Industry Co(RTM).

Component (II) can also be a mixture of two different Mg- and/orZn-compounds, for example

Mg-stearate and hydrotalcite (DHT-4A (RTM)),

Zn-stearate and hydrotalcite (DHT-4A (RTM)),

Mg-acetylacetonate and hydrotalcite (DHT-4A (RTM)),

Mg-oxide and hydrotalcite (DHT-4A (RTM)),

Mg-hydroxide and hydrotalcite (DHT-4A (RTM)),

Zn-hydroxide-carbonate and Mg-stearate,

Zn-hydroxide-carbonate and Zn-stearate,

Zn-hydroxide-carbonate and Mg-acetylacetonate,

Zn-hydroxide-carbonate and Mg-oxide,

Zn-hydroxide-carbonate and Zn-oxide,

Zn-hydroxide-carbonate and Mg-hydroxide,

hydrotalcite (REHEIS (RTM)) and Mg-stearate,

hydrotalcite (REHEIS (RTM)) and Zn-stearate,

hydrotalcite (REHEIS (RTM)) and Mg-oxide,

dolomite (Microdol Super (RTM)) and Zn-stearate,

dolomite (Microdol Super (RTM)) and Mg-stearate,

dolomite (Microdol Super (RTM)) and Zn-oxide,

dolomite (Microdol Super (RTM)) and Mg-hydroxide,

Mg-stearate and Zn-stearate,

Mg-stearate and Zn-acetylacetonate,

Mg-stearate and Mg-oxide,

Mg-stearate and Zn-oxide,

Mg-stearate and Mg-hydroxide,

Zn-stearate and Mg-acetate,

Zn-stearate and Mg-oxide,

Zn-stearate and Mg-hydroxide,

Mg-acetylacetonate and Zn-acetylacetonate,

Mg-acetylacetonate and Mg-oxide,

Mg-acetylacetonate and Zn-oxide,

Mg-acetylacetonate and Mg-hydroxide,

Zn-acetylacetonate and Mg-oxide,

Zn-acetylacetonate and Zn-oxide, or

Mg-oxide and Zn-oxide.

In this case, the two different compounds of component (II) may bepresent in a weight ratio of 1:10 to 10:1.

A preferred embodiment of this invention relates to a stabilizer mixturewherein the compound(s) of component (II) is (are) selected from thegroup consisting of Mg carboxylates, Zn carboxylates, Mg oxides, Znoxides, Mg hydroxides, Zn hydroxides, Mg carbonates and Zn carbonates.

Another preferred embodiment of this invention relates to a stabilizermixture wherein component (II) is a Mg carboxylate, a Zn carboxylate, ahydrotalcite, or a mixture of a Mg carboxylate and a hydrotalcite.

A particularly preferred embodiment of this invention relates to astabilizer mixture wherein component (II) is Mg stearate, Zn stearate, ahydrotalcite, in particular DHT-4A (RTM), or a mixture of Mg stearateand a hydrotalcite.

Preferred examples of stabilizer mixtures according to the presentinvention are:

1. TINUVIN 622 (RTM)+CHIMASSORB 944 (RTM)+Mg stearate

2. TINUVIN 622 (RTM)+CHIMASSORB 119 (RTM)+Mg stearate

3. TINUVIN 622 (RTM)+CHIMASSORB 2020 (RTM)+Mg stearate

4. TINUVIN 622 (RTM)+CYASORB UV 3346 (RTM)+Mg stearate

5. TINUVIN 622 (RTM)+CYASORB UV 3529 (RTM)+Mg stearate

6. TINUVIN 622 (RTM)+UVASORB HA 88 (RTM)+Mg stearate

7. TINUVIN 622 (RTM)+UVINUL 5050 H (RTM)+Mg stearate

8. TINUVIN 622 (RTM)+ADK STAB LA 63 (RTM)+Mg stearate

9. TINUVIN 622 (RTM)+ADK STAB LA 68 (RTM)+Mg stearate

10. TINUVIN 622 (RTM)+UVASIL 299 HM (RTM)+Mg stearate

11. TINUVIN 622 (RTM)+TINUVIN 770 (RTM)+Mg stearate

12. TINUVIN 622 (RTM)+TINUVIN 765 (RTM)+Mg stearate

13. TINUVIN 622 (RTM)+TINUVIN 123 (RTM)+Mg stearate

14. TINUVIN 622 (RTM)+HOSTAVIN N 20 (RTM)+Mg stearate

15. TINUVIN 622 (RTM)+ADK STAB LA 52 (RTM)+Mg stearate

16. TINUVIN 622 (RTM)+ADK STAB LA 57 (RTM)+Mg stearate

17. TINUVIN 622 (RTM)+CYASORB UV 3581 (RTM)+Mg stearate

18. TINUVIN 622 (RTM)+CYASORB UV 3641 (RTM)+Mg stearate

19. TINUVIN 622 (RTM)+UVINUL 4050 H (RTM)+Mg stearate

20. TINUVIN 622 (RTM)+DASTIB 845 (RTM)+Mg stearate

21. TINUVIN 770 (RTM)+CHIMASSORB 944 (RTM)+Mg stearate

22. TINUVIN 770 (RTM)+CHIMASSORB 119 (RTM)+Mg stearate

23. TINUVIN 770 (RTM)+CHIMASSORB 2020 (RTM)+Mg stearate

24. TINUVIN 770 (RTM)+CYASORB UV 3346 (RTM)+Mg stearate

25. TINUVIN 770 (RTM)+CYASORB UV 3529 (RTM)+Mg stearate

26. TINUVIN 770 (RTM)+UVASORB HA 88 (RTM)+Mg stearate

27. TINUVIN 770 (RTM)+UVINUL 5050 H (RTM)+Mg stearate

28. TINUVIN 770 (RTM)+ADK STAB LA 63 (RTM)+Mg stearate

29. TINUVIN 770 (RTM)+ADK STAB LA 68 (RTM)+Mg stearate

30. TINUVIN 770 (RTM)+UVASIL 299 HM (RTM)+Mg stearate

31. TINUVIN 770 (RTM)+TINUVIN 765 (RTM)+Mg stearate

32. TINUVIN 770 (RTM)+TINUVIN 123 (RTM)+Mg stearate

33. TINUVIN 770 (RTM)+HOSTAVIN N 20 (RTM)+Mg stearate

34. TINUVIN 770 (RTM)+ADK STAB LA 52 (RTM)+Mg stearate

35. TINUVIN 770 (RTM)+ADK STAB LA 57 (RTM)+Mg stearate

36. TINUVIN 770 (RTM)+CYASORB UV 3581 (RTM)+Mg stearate

37. TINUVIN 770 (RTM)+CYASORB UV 3641 (RTM)+Mg stearate

38. TINUVIN 770 (RTM)+UVINUL 4050 H (RTM)+Mg stearate

39. TINUVIN 770 (RTM)+DASTIB 845 (RTM)+Mg stearate

40. CHIMASSORB 944 (RTM)+CHIMASSORB 119 (RTM)+Mg stearate

41. CHIMASSORB 944 (RTM)+CHIMASSORB 2020 (RTM)+Mg stearate

42. CHIMASSORB 944 (RTM)+CYASORB UV 3346 (RTM)+Mg stearate

43. CHIMASSORB 944 (RTM)+CYASORB UV 3529 (RTM)+Mg stearate

44. CHIMASSORB 944 (RTM)+UVASORB HA 88 (RTM)+Mg stearate

45. CHIMASSORB 944 (RTM)+UVINUL 5050 H (RTM)+Mg stearate

46. CHIMASSORB 944 (RTM)+ADK STAB LA 63 (RTM)+Mg stearate

47. CHIMASSORB 944 (RTM)+ADK STAB LA 68 (RTM)+Mg stearate

48. CHIMASSORB 944 (RTM)+UVASIL 299 HM (RTM)+Mg stearate

49. CHIMASSORB 944 (RTM)+TINUVIN 765 (RTM)+Mg stearate

50. CHIMASSORB 944 (RTM)+TINUVIN 123 (RTM)+Mg stearate

51. CHIMASSORB 944 (RTM)+HOSTAVIN N 20 (RTM)+Mg stearate

52. CHIMASSORB 944 (RTM)+ADK STAB LA 52 (RTM)+Mg stearate

53. CHIMASSORB 944 (RTM)+ADK STAB LA 57 (RTM)+Mg stearate

54. CHIMASSORB 944 (RTM)+CYASORB UV 3581 (RTM)+Mg stearate

55. CHIMASSORB 944 (RTM)+CYASORB UV 3641 (RTM)+Mg stearate

56. CHIMASSORB 944 (RTM)+UVINUL 4050 H (RTM)+Mg stearate

57. CHIMASSORB 944 (RTM)+DASTIB 845 (RTM)+Mg stearate

58. CHIMASSORB 119 (RTM)+CYASORB UV 3529 (RTM)+Mg stearate

59. CHIMASSORB 11 9 (RTM)+ADK STAB LA 63 (RTM)+Mg stearate

60. CHIMASSORB 119 (RTM)+TINUVIN 765 (RTM)+Mg stearate

61. CHIMASSORB 119 (RTM)+TINUVIN 123 (RTM)+Mg stearate

62. CHIMASSORB 119 (RTM)+ADK STAB LA 52 (RTM)+Mg stearate

63. CHIMASSORB 11 9 (RTM)+CYASORB UV 3641 (RTM)+Mg stearate

The formulations obtained by replacing in the formulations 2 to 63 Mgstearate by Zn stearate are also preferred. Further, the formulations 1to 66 wherein Mg stearate is replaced by DHT-4A or Mg oxide or bycombinations of the coadditives listed as component (II) are preferred.

Examples of the latter formulations are:

1. TINUVIN 622 (RTM)+CHIMASSORB 944 (RTM)+DHT-4A (RTM)+Mg stearate

2. TINUVIN 770 (RIM)+CHIMASSORB 944 (RIM)+DHT-4A (RIM)+Mg stearate

3. TINUVIN 622 (RTM)+CHIMASSORB 119 (RTM)+DHT-4A (RTM)+Mg stearate

4. TINUVIN 770 (RTM)+UVASORB HA 88 (RTM)+DHT-4A (RTM)+Mg stearate

5. TINUVIN 622 (RTM)+UVASORB HA 88 (RTM)+DHT-4A (RTM)+Mg stearate

6. TINUVIN 622 (RIM)+UVASIL 299 (RIM)+DHIAA (RIM)+Mg stearate

7. TINUVIN 622 (RTM)+CHIMASSORB 2020 (RTM)+DHT-4A (RTM)+Mg stearate

8. TINUVIN 770 (RTM)+CHIMASSORB 2020 (RIM)+DHT-4A (RIM)+Mg stearate

The commercial product TINUVIN 622 (RTM) corresponds to the compound ofthe formula (B-7-a).

The commercial product CHIMASSORB 944 (RTM) corresponds to the compoundof the formula (B-1-a) wherein R₆ is hydrogen.

The commercial product CHIMASSORB 119 (RTM) corresponds to the compoundof the formula (B-2-a) wherein R₁₃ is methyl.

The commercial product CHIMASSORB 2020 (RTM) corresponds to the compoundof the formula (B-1-b) wherein R₆ is hydrogen.

The commercial product CYASORB UV 3346 (RTM) corresponds to the compoundof the formula (B-1-d) wherein R₆ is hydrogen.

The commercial product CYASORB UV 3529 (RTM) corresponds to the compoundof the formula (B-1-d) wherein R₆ is methyl.

The commercial product UVASORB HA 88 (RTM) corresponds to the product(B-6-a) wherein R₃₂ is hydrogen.

The commercial product UVINUL 5050 H (RTM) corresponds to the compoundof the formula (B-4-a) wherein R₁₈ is hydrogen.

The commercial product ADK STAB LA 63 (RTM) corresponds to the compoundof the formula (B-5-a) wherein R₃₀ is methyl.

The commercial product ADK STAB LA 68 (RTM) corresponds to the compoundof the formula (B-5-a) wherein R₃₀ is hydrogen.

The commercial product UVASIL 299 (RTM) corresponds to the compound ofthe formula (B-3-a) wherein R₁₆ is hydrogen.

The commercial product TINUVIN 770 (RTM) corresponds to the compound ofthe formula (A-1-b) wherein E₁ is hydrogen.

The commercial product TINUVIN 765 (RTM) corresponds to the compound ofthe formula (A-1-b) wherein E₁ is methyl.

The commercial product TINUVIN 123 (RTM) corresponds to the compound ofthe formula (A-1-b) wherein E₁ is octyloxy.

The commercial product HOSTAVIN N 20 (RTM) corresponds to the compoundof the formula (A-3-a) wherein E₁₂ is hydrogen.

The commercial product ADK STAB LA 52 (RTM) corresponds to the compoundof the formula (A-1-d) wherein E₁ is methyl.

The commercial product ADK STAB LA 57 (RTM) corresponds to the compoundof the formula (A-1-d) wherein E₁ is hydrogen.

The commercial product CYASORB UV 3581 (RTM) corresponds to the compoundof the formula (A-6-a) wherein E₁₈ is hydrogen.

The commercial product CYASORB UV 3641 (RTM) corresponds to the compoundof the formula (A-6-a) wherein E₁₈ is methyl.

The commercial product UVINUL 4050 H (RTM) corresponds to the compoundof the formula (A-10-a) wherein E₂₉ is hydrogen.

The commercial product DASTIB 845 (RTM) corresponds to the compound ofthe formula (A-1-a) wherein E₁ is hydrogen.

A further preferred embodiment of this invention relates to a stabilizermixture containing additionally

(X-1) a pigment or

(X-2) an UV absorber or

(X-3) a pigment and an UV absorber.

The pigment (component (X-1)) may be an inorganic or organic pigment.

Examples of inorganic pigments are titanium dioxide, zinc oxide, carbonblack, cadmium sulfide, cadmium selenide, chromium oxide, iron oxide,lead oxide and so on.

Examples of organic pigments are azo pigments, anthraquinones,phthalocyanines, tetrachloroisoindolinones, quinacridones, isoindolines,perylenes, pyrrolopyrroles (such as Pigment Red 254) and so on.

All pigments described in “Gächter/Müller: Plastics Additives Handbook,3rd Edition, Hanser Publishers, Munich Vienna New York”, page 647 to659, point 11.2.1.1 to 11.2.4.2 can be used as component (X-1).

A particularly preferred pigment is titanium dioxide, optionally incombination with an organic pigment.

Examples of such organic pigments are:

C.I. (Colour Index) Pigment Yellow 93, C.I. Pigment Yellow 95, C.I.Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 155,C.I. Pigment Yellow 162, C.I. Pigment Yellow 168, C.I. Pigment Yellow180, C.I. Pigment Yellow 183, C.0. Pigment Red 44, C.I. Pigment Red 170,C.I. Pigment Red 202, C.I. Pigment Red 214, C.I. Pigment Red 254, C.I.Pigment Red 264, C.I. Pigment Red 272, C.I. Pigment Red 48:2, C.I.Pigment Red 48:3, C.I. Pigment Red 53:1, C.I. Pigment Red 57:1, C.I.Pigment Green 7, C.I. Pigment Blue 15:1, C.I. Pigment Blue 15:3 and C.I.Pigment Violet 19.

Examples of the UV absorber (component (X-2)) are a2-(2′-hydroxyphenyl)benzotriazole, a 2-hydroxybenzophenone, an ester ofsubstituted or unsubstituted benzoic acid, an acrylate, an oxamide, a2-(2-hydroxyphenyl)-1,3,5-triazine, a monobenzoate of resorcinol or aformamidine.

The 2-(2′-hydroxyphenyl)benzotriazole is e.g.2-(2′-hydroxy-5′-methylphenyl)-benzotriazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(5′-tert-butyl-2′-hydroxyphenyl)benzo-triazole,2-(2′-hydroxy-5′-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-methylphenyl)-5-chloro-benzotriazole,2-(3′-sec-butyl-5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-4′-octyloxyphenyl)benzotriazole,2-(3′,5′-di-tert-amyl-2′-hydroxyphenyl)benzotriazole,2-(3′,5′-bis-(α,α-dimethylbenzyl)-2′-hydroxyphenyl)benzotriazole,mixture of2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylmethyl)phenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)-carbonylethyl]-2′-hydroxyphenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′--hydroxy-5′-(2-methoxycarbonylethyl)phenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)benzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonyl-ethyl]-2′-hydroxyphenyl)benzotriazole,2-(3′-dodecyl-2′-hydroxy-5′-methylphenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-isooctyloxycarbonylethyl)phenylbenzotriazole,2,2′--methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-ylphenol]or the transesterification product of2-[3′-tert-butyl-5′-(2-methoxycarbonylethyl)-2′-hydroxyphenyl]-2H-benzotriazolewith polyethylene glycol 300; [R—CH₂CH₂—COO(CH₂)₃-]₂ whereR=3′-tert-butyl-4′-hydroxy-5′-2H-benzotriazole-2-ylphenyl.

2-(3′,5′-Di-tert-butyl-2′-hydroxyphenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-methylphenyl)-5-chloro-benzotriazole and2-(3′,5′-di-tert-amyl-2′-hydroxyphenyl)-benzotriazole are preferred.

The 2-hydroxybenzophenone is for example the 4-hydroxy, 4-methoxy,4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2′,4′-trihydroxy or2′-hydroxy-4,4′-dimethoxy derivatives.

2-Hydroxy-4-octyloxybenzophenone is preferred.

The ester of a substituted or unsubstituted benzoic acid is for example4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenylsalicylate, dibenzoyl resorcinol, bis(4-tert-butylbenzoyl) resorcinol,benzoyl resorcinol, 2,4-di-tertbutylphenyl3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl3,5-di-tert-butyl-4-hydroxy-benzoate or 2-methyl-4,6-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate.

2,4-Di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate andhexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate are preferred.

The acrylate is for example ethyl (α-cyano-β,β-diphenylacrylate,isooctyl α-cyano-β,β-di-phenylacrylate, methyl α-carbomethoxycinnamate,methyl (α-cyano-β-methyl-p-methoxy-cinnamate, butylα-cyano-β-methyl-p-methoxy-cinnamate, methylα-carbomethoxy-p-methoxycinnamate orN-(β-carbomethoxy-p-cyanovinyl)-2-methylindoline.

The oxamide is for example 4,4′-dioctyloxyoxanilide,2,2′-diethoxyoxanilide, 2,2′-didodectyloxy-5,5′-di-butoxanilide,2,2′-didodecyloxy-5,5′-di-tert-butoxanilide, 2-ethoxy-2′-ethyloxanilide,N,N′-bis(3-dimethylaminopropyl)oxamide,2-ethoxy-5-tert-butyl-2′-ethoxanilide or its mixture with2-ethoxy-2′-ethyl-5,4′-di-tert-butoxanilide or mixtures of ortho- andpara-methoxy-disubstituted oxanilides or mixtures of o- andp-ethoxy-disubsituted oxanilides.

The 2-(2-hydroxyphenyl)-1,3,5-triazine is for example2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2,4-dihydroxyphenyl)-4,6-(2,4-dimethylphenyl)-1,3,5-triazine,2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-butyloxy-propyloxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-octyloxy-propyloxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine,2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxy-phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxy-propoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine,2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine,2,4,6-tris[2-hydroxy-4-(3-butoxy-2--hydroxy-propoxy)phenyl]-1,3,5-triazineor 2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine.

2-(2-Hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazineand 2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine arepreferred.

The monobenzoate of resorcinol is for example the compound of theformula:

The formamidine is for example the compound of the formula:

The UV absorber is in particular a 2-(2′-hydroxyphenyl)benzotriazole, a2-hydroxybenzophenone or a hydroxyphenyltriazine.

A further preferred embodiment of this invention relates to a stabilizermixture which additionally contains as a further component (XX) anorganic salt of Ca, an inorganic salt of Ca, Ca oxide or Ca hydroxide.

Examples of an organic salt of Ca are Ca-stearate, Ca-laurate,Ca-lactate and Ca-stearoyl-lactate.

Examples of an inorganic salt of Ca are CaCO₃, CaCl₂, CaF₂, Ca₃(PO₄)₂,CaHPO₄, Ca(PO₃)₂, Ca₂R₂₀ ₇, CaSO₄ and CaSiO₃.

Further preferred examples of stabilizer mixtures according to thepresent invention are:

a. TINUVIN 622 (RTM)+CHIMASSORB 944 (RTM)+Mg stearate+Ca stearate

b. TINUVIN 770 (RTM)+CHIMASSORB 944 (RTM)+Mg stearate+Ca stearate

c. TINUVIN 622 (RTM)+CHIMASSORB 119 (RTM)+Mg stearate+Ca stearate

d. TINUVIN 770 (RTM)+UVASORB HA 88 (RTM)+Mg stearate+Ca stearate

e. TINUVIN 622 (RTM)+UVASORB HA 88 (RTM)+Mg stearate+Ca stearate

f. TINUVIN 622 (RTM)+UVASIL 299 (RTM)+Mg stearate+Ca stearate

g. TINUVIN 622 (RTM)+CHIMASSORB 2020 (RTM)+Mg stearate+Ca stearate

h. TINUVIN 770 (RTM)+CHIMASSORB 2020 (RTM)+Mg stearate+Ca stearate

i. TINUVIN 622 (RTM)+CHIMASSORB 944 (RTM)+DHT-4A (RTM)+Ca stearate

j. TINUVIN 770 (RTM)+CHIMASSORB 944 (RTM)+DHT-4A (RTM)+Ca stearate

k. TINUVIN 622 (RTM)+CHIMASSORB 119 (RTM)+DHT-4A (RTM)+Ca stearate

i. TINUVIN 770 (RTM)+UVASORB HA 88 (RTM)+DHT-4A (RTM)+Ca stearate

m. TINUVIN 622 (RTM)+UVASORB HA 88 (RTM)+DHT-4A (RTM)+Ca stearate

n. TINUVIN 622 (RTM)+UVASIL 299 (RTM)+DHT-4A (RTM)+Ca stearate

o. TINUVIN 622 (RTM)+CHIMASSORB 2020 (RTM)+DHT-4A (RTM)+Ca stearate

p. TINUVIN 770 (RTM)+CHIMASSORB 2020 (RTM)+DHT-4A (RTM)+Ca stearate

The stabilizer mixture according to this invention is suitable forstabilizing organic materials against degradation induced by light, heator oxidation. Examples of such organic materials are the following:

1. Polymers of monoolefins and diolefins, for example polypropylene,polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyisoprene orpolybutadiene, as well as polymers of cycloolefins, for instance ofcyclopentene or norbornene, polyethylene (which optionally can becrosslinked), for example high density polyethylene (HDPE), high densityand high molecular weight polyethylene (HDPE-HMW), high density andultrahigh molecular weight polyethylene (HDPE-UHMW), medium densitypolyethylene (MDPE), low density polyethylene (LDPE), linear low densitypolyethylene (LLDPE), (VLDPE) and (ULDPE), or polyvinyl cyclohexane.

Polyolefins, i.e. the polymers of monoolefins exemplified in thepreceding paragraph, preferably polyethylene and polypropylene, can beprepared by different, and especially by the following, methods:

a) radical polymerisation (normally under high pressure and at elevatedtemperature).

b) catalytic polymerisation using a catalyst that normally contains oneor more than one metal of groups IVb, Vb, VIb or VIII of the PeriodicTable. These metals usually have one or more than one ligand, typicallyoxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenylsand/or aryls that may be either π- or σ-coordinated. These metalcomplexes may be in the free form or fixed on substrates, typically onactivated magnesium chloride, titanium(II) chloride, alumina or siliconoxide. These catalysts may be soluble or insoluble in the polymerisationmedium. The catalysts can be used by themselves in the polymerisation orfurther activators may be used, typically metal alkyls, metal hydrides,metal alkyl halides, metal alkyl oxides or metal alkyloxanes, saidmetals being elements of groups Ia, IIa and/or IIIa of the PeriodicTable. The activators may be modified conveniently with further ester,ether, amine or silyl ether groups. These catalyst systems are usuallytermed Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont),metallocene or single site catalysts (SSC).

2. Mixtures of the polymers mentioned under 1), for example mixtures ofpolypropylene with polyisobutylene, polypropylene with polyethylene (forexample PP/HDPE, PP/LDPE) and mixtures of different types ofpolyethylene (for example LDPE/HDPE).

3. Copolymers of monoolefins and diolefins with each other or with othervinyl monomers, for example ethylene/propylene copolymers, linear lowdensity polyethylene (LLDPE) and mixtures thereof with low densitypolyethylene (LDPE), propylene/but-1-ene copolymers,propylene/isobutylene copolymers, ethylene/but-1-ene copolymers,ethylene/hexene copolymers, ethylene/methylpentene copolymers,ethylene/heptene copolymers, ethylene/octene copolymers,propylene/butadiene copolymers, isobutylene/isoprene copolymers,ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylatecopolymers, ethylene/vinyl acetate copolymers and their copolymers withcarbon monoxide or ethylene/acrylic acid copolymers and their salts(ionomers) as well as terpolymers of ethylene with propylene and a dienesuch as hexadiene, dicyclopentadiene or ethylidene-norbornene; andmixtures of such copolymers with one another and with polymers mentionedin 1) above, for example polypropylene/ethylene-propylene copolymers,LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acidcopolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or randompolyalkylene/carbon monoxide copolymers and mixtures thereof with otherpolymers, for example polyamides.

4. Hydrocarbon resins (for example C₅-C₉) including hydrogenatedmodifications thereof (e.g. tackifiers) and mixtures of polyalkylenesand starch.

5. Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene).

6. Copolymers of styrene or cc-methylstyrene with dienes or acrylicderivatives, for example styrene/butadiene, styrene/acrylonitrile,styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate,styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride,styrene/acrylonitrile/methyl acrylate; mixtures of high impact strengthof styrene copolymers and another polymer, for example a polyacrylate, adiene polymer or an ethylene/propylene/diene terpolymer; and blockcopolymers of styrene such as styrene such as styrene/butadienestyrene,styrene/isoprene/styrene, styrene/ethylene/butylene/styrene orstyrene/ethylene/propylene/styrene.

7. Graft copolymers of styrene or oc-methylstyrene, for example styreneon polybutadiene, styrene on polybutadiene-styrene orpolybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (ormethacrylonitrile) on polybutadiene; styrene, acrylonitrile and methylmethacrylate on polybutadiene; styrene and maleic anhydride onpolybutadiene; styrene, acrylonitrile and maleic anhydride or maleimideon polybutadiene; styrene and maleimide on polybutadiene; styrene adnalkyl acrylates or methacrylates on polybutadiene; styrene andacrylonitrile on ethylene/propylene/diene terpolymers; styrene andacrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styreneand acrylonitrile on acrylate/butadiene copolymers, as well as mixturesthereof with the copolymers listed under 6), for example the copolymermixtures known as ABS, MBS, ASA or AES polymers.

8. Halogen-containing polymers such as polychloroprene, chlorinatedrubbers, chlorinated and brominated copolymer of isobutylene-isoprene(halobutyl rubber), chlorinated or sulfochlorinated polyethylene,copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo-and copolymers, especially polymers of halogen-containing vinylcompounds, for example polyvinyl chloride, polyvinylidene chloride,polyvinyl fluoride, polyvinylidene fluoride, as well as copolymersthereof such as vinyl chloride/vinylidene chloride, vinyl chloride/vinylacetate or vinylidene chloride/vinyl acetate copolymers.

9. Polymers derived from α,β-unsaturated acids and derivatives thereofsuch as polyacrylates and polymethacrylates; polymethyl methacrylates,polyacrylamides and polyacrylonitriles, impact-modified with butylacrylate.

10. Copolymers of the monomers mentioned under 9) with each other orwith other unsaturated monomers, for example acrylonitrile/butadienecopolymers, acrylonitrile/alkyl acrylate copolymers,acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halidecopolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.

11. Polymers derived from unsaturated alcohols and amines or the acylderivatives or acetals thereof, for example polyvinyl alcohol, polyvinylacetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate,polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well astheir copolymers with olefins mentioned in 1) above.

12. Homopolymers and copolymers of cyclic ethers such as polyalkyleneglycols, polyethylene oxide, polypropylene oxide or copolymers thereofwith bisglycidyl ethers.

13. Polyacetals such as polyoxymethylene and those polyoxymethyleneswhich contain ethylene oxide as a comonomer; polyacetals modified withthermoplastic polyurethanes, acrylates or MBS.

14. Polyphenylene oxides and sulfides, and mixtures of polyphenyleneoxides with styrene polymers or polyamides.

15. Polyurethanes derived from hydroxyl-terminated polyethers,polyesters or polybutadienes on the one hand and aliphatic or aromaticpolyisocyanates on the other, as well as precursors thereof.

16. Polyamides and copolyamides derived from diamines and dicarboxylicacids and/or from aminocarboxylic acids or the corresponding lactams,for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12,4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides startingfrom m-xylene diamine and adipic acid; polyamides prepared fromhexamethylenediamine and isophthalic or/and terephthalic acid and withor without an elastomer as modifier, for examplepoly-2,4,4-trimethylhexamethylene terephthalamide of poly-m-phenyleneisophthalamide; and also block copolymers of the aforementionedpolyamides with polyolefins, olefin copolymers, ionomers or chemicallybonded or grafted elastomers; or with polyethers, e.g. with polyethyleneglycol, polypropylene glycol or polytetramethylene glycol; as well aspolyamides or copolyamides modified with EPDM or ABS; and polyamidescondensed during processing (RIM polyamide systems).

17. Polyureas, polyimides, polyamide-imides, polyetherimids,polyesterimids, polyhydantoins and polybenzimidazoles.

18. Polyesters derived from dicarboxylic acids and diols and/or fromhydroxycarboxylic acids or the corresponding lactones, for examplepolyethylene terephthalate, polybutylene terephthalate,poly-1,4-dimethylolcyclohexane terephthalate, polyalkylene naphthalate(PAN) and polyhydroxybenzoates, as well as block copolyether estersderived from hydroxyl-terminated polyethers; and also polyestersmodified with polycarbonates or MBS.

19. Polycarbonates and polyester carbonates.

20. Polysulfones, polyether sulfones and polyether ketones.

21. Crosslinked polymers derived from aldehydes on the one hand andphenols, ureas and melamines on the other hand, such asphenol/formaldehyde resins, urea/formaldehyde resins andmelamine/formaldehyde resins. and melamine/fomaldehyde resins.

22. Drying and non-drying alkyd resins.

23. Unsaturated polyester resins derived from copolyesters of saturatedand unsaturated dicarboxylic acids with polyhydric alcohols and vinylcompounds as crosslinking agents, and also halogen-containingmodifications thereof of low flammability.

24. Crosslinkable acrylic resins derived from substituted acrylates, forexample epoxy acrylates, urethane acrylates or polyester acrylates.

25. Alkyd resins, polyester resins and acrylate resins crosslinked withmelamine resins, urea resins, isocyanates, isocyanurates,polyisocyanates or epoxy resins.

26. Crosslinked epoxy resins derived from aliphatic, cycloaliphatic,heterocyclic or aromatic glycidyl compounds, e.g. products of diglycidylethers of bisphenol A and bisphenol F, which are crosslinked withcustomary hardeners such as anhydrides or amines, with or withoutaccelerators.

27. Natural polymers such as cellulose, rubber, gelatin and chemicallymodified homologous derivatives thereof, for example cellulose acetates,cellulose propionates and cellulose butyrates, or the cellulose etherssuch as methyl cellulose; as well as rosins and their derivatives.

28. Blends of the aforementioned polymers (polyblends), for examplePP/EPDM, Polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS,PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR,PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 andcopolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.

29. Naturally occurring and synthetic organic materials which are puremonomeric compounds or mixtures of such compounds, for example mineraloils, animal and vegetable fats, oil and waxes, or oils, fats and waxesbased on synthetic esters (e.g. phthalates, adipates, phosphates ortrimellitates) and also mixtures of synthetic esters with mineral oilsin any weight ratios, typically those used as spinning compositions, aswell as aqueous emulsions of such materials.

30. Aqueous emulsions of natural or synthetic rubber, e.g. natural latexor latices of carboxylated styrene/butadiene copolymers.

This invention therefore additionally relates to a compositioncomprising an organic material subject to degradation induced by light,heat or oxidation and the stabilizer mixture described above.

The compositions according to the present invention preferably do notcontain a mineral oil.

Further, the organic material is preferably different from polyethylene,when component (I) is the combination of the compounds (B-1-a-1) and(B-7-a), in particular the combination of a compound of the class (β-1)and a compound of the class (β-7); and, at the same time, component (II)is Zn carboxylate, in particular an organic salt of Zn.

A preferred embodiment of the present invention relates to polypropylenecontaining a compound of the formula (B-1), a compound of the formula(B-7) and a Zn-carboxylate;

in which

R₁, R₃, R₄ and R₅ independently of one another are hydrogen,C₁-C₁₂alkyl, C₅-C₁₂cycloalkyl, C₁-C₄-alkyl-substituted C₅-C₁₂cycloalkyl,phenyl, phenyl which is substituted by —OH and/or

C₁-C₁₀alkyl; C₇-C₉phenylalkyl, C₇-C₉phenylalkyl which is substituted onthe phenyl radical by —OH and/or C₁-C₁₀alkyl; or a group of the formula(b-I):

R₂ is C₂-C₁₈alkylene, C₅-C₇cycloalkylene orC₁-C₄alkylenedi(B₅—C₇cycloalkylene), or

the radicals R₁, R₂ and R₃, together with the nitrogen atoms to whichthey are bonded, perform a 5- to 10-membered heterocyclic ring, or

R₄ and R₅, together with the nitrogen atom to which they are bonded,form a 5- to 10-membered heterocyclic ring,

R₆ is hydrogen, C₁-C₈alkyl, O⁻, —OH, —CH₂CN, C₁-C₁₈alkoxy,C₅-C₁₂cycloalkoxy, C₃-C₈alkenyl,

C₇-C₉phenylalkyl unsubstituted or substituted on the phenyl by 1, 2 or 3C₁-C₄alkyl; or

C₁-C₈acyl, and

b₁ is a number from 2 to 50,

with the proviso that at least one of the radicals R₁, R₃, R₄ and R₅ isa group of the formula (b-I);

wherein A₁ is hydrogen or C₁-C₄alkyl,

A₂ is a direct bond or C₁-C₁₀alkylene, and

n₁ is a number from 2 to 50.

Another embodiment of the present invention is a method for stabilizingan organic material against degradation induced by light, heat oroxidation, which comprises incorporating into the organic material thestabilizer mixture described above.

The organic material is preferably a synthetic polymer, in particularfrom one of the above groups. Polyolefins are preferred andpolyethylene, polypropylene, a polyethylene copolymer or a polypropylenecopolymer are particularly preferred.

The components (I), (II) and optionally (X-1) and/or (X-2), as well asoptionally component (XX) may be added to the organic material to bestabilized either individually or mixed with one another.

The total amount of the two different sterically hindered aminecompounds (component (I)) in the organic material to be stabilized ispreferably 0.005 to 5%, in particular 0.01 to 1% or 0.05 to 1%, relativeto the weight of the organic material.

The Mg and/or Zn compounds (component (II)) are present in the organicmaterial in a total amount of preferably 0.005 to 1%, in particular 0.05to 0.2%, relative to the weight of the organic material.

The pigment (component (X-1)) is optionally present in the organicmaterial in an amount of preferably 0.01 to 10%, in particular 0.05 to1%, relative to the weight of the organic material.

The UV absorber (component (X-2)) is optionally present in the organicmaterial in an amount of preferably 0.01 to 1%, in particular 0.05 to0.5%, relative to the weight of the organic material.

The total amount of component (X-3) (the pigment in combination with theUV absorber) is preferably 0.01 to 10%, relative to the weight of theorganic material. The weight ratio of the UV absorber to the pigment isfor example 2:1 to 1:10.

When the pigment used is titanium dioxide in combination with an organicpigment as described above, titanium dioxide is preferably present inthe organic material in an amount of 0.01 to 5%, relative to the weightof the organic material, and the organic pigment may be present in anamount of, for example, 0.01 to 2%, relative to the weight of theorganic material.

The Ca compound (component (XX)) is optionally present in the organicmaterial in an amount of e.g. 0.005 to 1%, preferably 0.05 to 0.2%.

The weight ratio of the two different sterically hindered aminecompounds forming component (I) is for example 1:10 to 10:1, preferably1:5 to 5:1, in particular 1:2 to 2:1.

The weight ratio of the components (I):(II) is for example 1:10 to 20:1,preferably 1:5 to 5:1, in particular 1:2 to 2:1.

The weight ratio of the components (I):(X-1) is for example 1:10 to10:1, preferably 1:5 to 5:1, in particular 1:2 to 2:1.

The weight ratio of the components (I):(X-2) is for example 1:5 to 5:1,preferably 1:2 to 2:1.

The weight ratio of the components (I) (X-3) is for example 1:10 to10:1, preferably 1:5 to 5:1, in particular 1:2 to 2:1.

The weight ratio of the components (I):(XX) is for example 1:10 to 10:1,preferably 1:5 to 5:1, in particular 1:2 to 2:1.

The above components can be incorporated into the organic material to bestabilized by known methods, for example before or during shaping or byapplying the dissolved or dispersed compounds to the organic material,if necessary with subsequent evaporation of the solvent. The componentscan be added to the organic material in the form of a powder, granulesor a masterbatch, which contains these components in, for example, aconcentration of from 2.5 to 25% by weight.

If desired, the components (I), (II) and optionally (X-1) and/or (X-2),as well as component (XX) can be melt blended with each other beforeincorporation in the organic material. They can be added to a polymerbefore or during the polymerization or before the crosslinking.

The materials stabilized according to this invention can be used in awide variety of forms, for example as films, fibres, tapes, mouldingcompositions, profiles or as binders for paints, adhesives or putties.

Examples of Processing or Transformation of the Plastics According tothe Present Invention are:

Injection blow molding, extrusion, blow molding, rotomolding, in molddecoration (back injection), slush molding, injection molding,co-injection molding, forming, compression molding, pressing, filmextrusion (cast film; blown film), fiber spinning (woven, non-woven),drawing (uniaxial, biaxial), annealing, deep drawing, calandering,mechanical transformation, sintering, coextrusion, coating, lamination,crosslinking (radiation, peroxide, silane), vapor deposition, weldtogether, glue, vulkanization, thermoforming, pipe extrusion, profileextrusion, sheet extrusion; sheet casting, spin coating, strapping,foaming, recycling/rework, extrusion coating, visbreaking (peroxide,thermal), fiber melt blown, spun bonded, surface treatment (coronadischarge, flame, plasma), sterilization (by gamma rays, electronbeams), cast polymerization (R&M process, RAM extrusion), gel-coating,tape extrusion, GMT-process, SMC-process, plastisol, and dipping (PVC,latex).

The Plastics According to the Present Invention may be Used for thePreparation of:

I-1) Floating devices, marine applications, pontoons, buoys, plasticlumber for decks, piers, boats, kayaks, oars, and beach reinforcements.

I-2) Automotive applications, in particular bumpers, dashboards,battery, rear and front linings, moldings parts under the hood, hatshelf, trunk linings, interior linings, air bag covers, electronicmoldings for fittings (lights), panes for dashboards, headlamp glass,instrument panel, exterior linings, upholstery, automotive lights, headlights, parking lights, rear lights, stop lights, interior and exteriortrims; door panels; gas tank; glazing front side; rear windows; seatbacking, exterior panels, wire insulation, profile extrusion forsealing, cladding, pillar covers, chassis parts, exhaust systems, fuelfilter/filler, fuel pumps, fuel tank, body side mouldings, convertibletops, exterior mirrors, exterior trim, fasteners/fixings, front endmodule, glass, hinges, lock systems, luggage/roof racks, pressed/stampedparts, seals, side impact protection, sound deadener/insulator andsunroof.

I-3) Road traffic devices, in particular sign postings, posts for roadmarking, car accessories, warning triangles, medical cases, helmets,tires.

I-4) Devices for plane, railway, motor car (car, motorbike) includingfurnishings.

I-5) Devices for space applications, in particular rockets andsatellites, e.g. reentry shields.

I-6) Devices for architecture and design, mining applications, acousticquietized systems, street refuges, and shelters.

II-1) Appliances, cases and coverings in general and electric/electronicdevices (personal computer, telephone, handy, printer, television-sets,audio and video devices), flower pots, satellite TV bowl, and paneldevices.

II-2) Jacketing for other materials such as steel or textiles.

II-3) Devices for the electronic industry, in particular insulation forplugs, especially computer plugs, cases for electric and electronicparts, printed boards, and materials for electronic data storage such aschips, check cards or credit cards.

II-4) Electric appliances, in particular washing machines, tumblers,ovens (microwave oven), dish-washers, mixers, and irons.

II-5) Covers for lights (e.g. street-lights, lamp-shades).

II-6) Applications in wire and cable (semi-conductor, insulation andcable-jacketing).

II-7) Foils for condensers, refrigerators, heating devices, airconditioners, encapsulating of electronics, semi-conductors, coffeemachines, and vacuum cleaners.

III-1) Technical articles such as cogwheel (gear), slide fittings,spacers, screws, bolts, handles, and knobs.

III-2) Rotor blades, ventilators and windmill vanes, solar devices,swimming pools, swimming pool covers, pool liners, pond liners, closets,wardrobes, dividing walls, slat walls, folding walls, roofs, shutters(e.g. roller shutters), fittings, connections between pipes, sleeves,and conveyor belts.

III-3) Sanitary articles, in particular shower cubicles, lavatory seats,covers, and sinks.

III-4) Hygienic articles, in particular diapers (babies, adultincontinence), feminine hygiene articles, shower curtains, brushes,mats, tubs, mobile toilets, tooth brushes, and bed pans.

III-5) Pipes (cross-linked or not) for water, waste water and chemicals,pipes for wire and cable protection, pipes for gas, oil and sewage,guttering, down pipes, and drainage systems.

III-6) Profiles of any geometry (window panes) and siding.

III-7) Glass substitutes, in particular extruded plates, glazing forbuildings (monolithic, twin or multiwall), aircraft, schools, extrudedsheets, window film for architectural glazing, train, transportation,sanitary articles, and greenhouse.

III-8) Plates (walls, cutting board), extrusion-coating (photographicpaper, tetrapack and pipe coating), silos, wood substitute, plasticlumber, wood composites, walls, surfaces, furniture, decorative foil,floor coverings (interior and exterior applications), flooring, duckboards, and tiles.

III-9) Intake and outlet manifolds.

III-10) Cement-, concrete-, composite-applications and covers, sidingand cladding, hand rails, banisters, kitchen work tops, roofing, roofingsheets, tiles, and tarpaulins.

IV-1) Plates (walls and cutting board), trays, artificial grass,astroturf, artificial covering for stadium rings (athletics), artificialfloor for stadium rings (athletics), and tapes.

IV-2) Woven fabrics continuous and staple, fibers (carpets/hygienicarticles/geotextiles/monofilaments; filters; wipes/curtains(shades)/medical applications), bulk fibers (applications such asgown/protection clothes), nets, ropes, cables, strings, cords, threads,safety seat-belts, clothes, underwear, gloves; boots; rubber boots,intimate apparel, garments, swimwear, sportswear, umbrellas (parasol,sunshade), parachutes, paraglides, sails, “balloon-silk”, campingarticles, tents, airbeds, sun beds, bulk bags, and bags.

IV-3) Membranes, insulation, covers and seals for roofs, tunnels, dumps,ponds, dumps, walls roofing membranes, geomembranes, swimming pools,curtains (shades)/sun-shields, awnings, canopies, wallpaper, foodpacking and wrapping (flexible and solid), medical packaging (flexible &solid), airbags/safety belts, arm- and head rests, carpets, centreconsole, dashboard, cockpits, door, overhead console module, door trim,headliners, interior lighting, interior mirrors, parcel shelf, rearluggage cover, seats, steering column, steering wheel, textiles, andtrunk trim.

V) Films (packaging, dump, laminating, agriculture and horticulture,greenhouse, mulch, tunnel, silage), bale wrap, swimming pools, wastebags, wallpaper, stretch film, raffia, desalination film, batteries, andconnectors.

VI-1) Food packing and wrapping (flexible and solid), BOPP, BOPET,bottles.

VI-2) Storage systems such as boxes (crates), luggage, chest, householdboxes, pallets, shelves, tracks, screw boxes, packs, and cans.

VI-3) Cartridges, syringes, medical applications, containers for anytransportation, waste baskets and waste bins, waste bags, bins, dustbins, bin liners, wheely bins, container in general, tanks forwater/used water/chemistry/gas/oil/gasoline/diesel; tank liners, boxes,crates, battery cases, troughs, medical devices such as piston,ophthalmic applications, diagnostic devices, and packing forpharmaceuticals blister.

VII-1) Extrusion coating (photo paper, tetrapack, pipe coating),household articles of any kind (e.g. appliances, thermos bottle/clotheshanger), fastening systems such as plugs, wire and cable clamps,zippers, closures, locks, and snap-closures.

VII-2) Support devices, articles for the leisure time such as sports andfitness devices, gymnastics mats, ski-boots, inline-skates, skis, bigfoot, athletic surfaces (e.g. tennis grounds); screw tops, tops andstoppers for bottles, and cans.

VII-3) Furniture in general, foamed articles (cushions, impactabsorbers), foams, sponges, dish clothes, mats, garden chairs, stadiumseats, tables, couches, toys, building kits (boards/figures/balls),playhouses, slides, and play veh

VII-4) Materials for optical and magnetic data storage.

VII-5) Kitchen ware (eating, drinking, cooking, storing).

VII-6) Boxes for CD's, cassettes and video tapes; DVD electronicarticles, office supplies of any kind (ball-point pens, stamps andink-pads, mouse, shelves, tracks), bottles of any volume and content(drinks, detergents, cosmetics including perfumes), and adhesive tapes.

VII-7) Footwear (shoes/shoe-soles), insoles, spats, adhesives,structural adhesives, food boxes (fruit, vegetables, meat, fish),synthetic paper, labels for bottles, couches, artificial joints (human),printing plates (flexographic), printed circuit boards, and displaytechnologies.

VII-8) Devices of filled polymers (talc, chalk, china clay (kaolin),wollastonite, pigments, carbon black, TiO₂, mica, nanocomposites,dolomite, silicates, glass, asbestos).

The stabilized material may additionally also contain variousconventional additives, for example:

1. Antioxidants

1.1. Alkylated monophenols, for example2,6-di-tert-butyl-4-methylphenol, 2--tert-butyl-4,6-dimethylphenol,2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol,2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol,2-(α-methylcyclohexyl)-4,6-dimethylphenol,2,6-dicyclopentyl-4-methylphenol,2(α-methylcyclohexyl)-4-dimethylphenol, 2,6-dioctadecyl-4-methylphenol,2,4,6-tricyclohexylphenyl, 2,6-di-tert-butyl-4-methoxymethylphenol,nonylphenols which are linear or branched in the side chains, forexample, 2,6-di-nonyl-4-methyl-phenol,2,4-dimethyl-6-(1′-methylundec-1′-yl)phenol,2,4-dimethyl-6-(1′-methylheptadec-1′-yl)phenol,2,4-dimethyl-6-(1′-methyltridec-1′-yl)phenol, and mixtures thereof.

1.2. Alkylthiomethylphenols, for example2,4-dioctylthiomethyl-6-tert-butylphenol,2,4-dioctylthiomethyl-6-methylphenol,2,4-dioctylthiomethyl-6-ethylphenol,2,6-di-dodecylthiomethyl-4-nonylphenol.

1.3. Hydroquinones and alkylated hydroquinones, for example2,6-di-tert-butyl-4--methoxyphenol, 2,5-di-tert-butylhydroquinone,2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol,2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole,3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenylstearate, bis(3,5-di-tert-butyl-4-hydroxyphenyl) adipate.

1.4. Tocopherols, for example α-tocopherol, β-tocopherol, γ-tocopherol,δ-tocopherol and mixtures thereof (Vitamin E

1.5. Hydroxylated thiodiphenyl ethers, for example2,2′-thiobis(6-tert-butyl-4-methylphenol), 2,2′-thiobis(4-octylphenol),4,4′-thiobis(6-tert-butyl-3-methylphenol),4,4′-thiobis(6-tert-butyl-2-methylphenol),4,4′-thiobis-(3,6-di-sec-amylphenol),4,4′-bis-(2,6-dimethyl-4-hydroxyphenol) disulfide.

1.6. Alkylidenebisphenols, for example2,2′-methylenebis(6-tert-butyl-4-methylphenol),2,2′-methylenebis(6-tert-butyl-4-ethylphenol),2,2′-methylenebis[4-methyl-6-(α-methylcyclohexyl)phenol],2,2′-methylenebis(4-methyl-6-cyclohexylphenol),2,2′-methylenebis(6-nonyl-4-methylphenol),2,2′-methylenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(4,6-di-tert-butylphenyl),2,2′-ethylenebis(6-di-tert-butyl-4-isobutylphenol),2,2′-methylenebis[6-(α-methylbenzyl)-4-nonylphenol],2,2′-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol],4,4′-methylenebis(2,6-di-tert-butylphenol),4,4′-methylenebis(6-di-tert-2-methylphenol),1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol,1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,1,1-bis(5-tert-butyl-4-hydroxy-2-methyl-phenyl)-3-n-dodecylmercaptobutane,ethylene glycol bis[3,3-bis(3′-tert-butyl-4′-hydroxyphenyl)butyrate],bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene,bis[2-(3′-tert-butyl-2′-hydroxy-5′-methylphenyl)-6-tert-butyl-4-methylphenyl]terephthalate,1,1-bis-(3,5-dimethyl-2-hydroxy-phenyl)butane,2,2-bis-(3,5-di-tert-butyl-4-hydroxyphenyl)propane,2,2-bis-(5-tert--butyl-4-hydroxy2-methylphenyl)-4-n-dodecylmercaptobutane,1,1,5,5-tetra-(5-tert--butyl-4-hydroxy2-methylphenyl)pentane.

1.7. O-, N- and S-benzyl compounds, for example3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydibenzyl ether,octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate,tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate,tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine,bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterphthalate,bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide,isooctyl-3,5di-tert-butyl-4--hydroxybenzylmercaptoacetate.

1.8. Hydroxybenzylated malonates, for exampledioctadecyl-2,2-bis-(3,5-di-tert--butyl-2-hydroxybenzyl)-malonate,di-octadecyl-2-(3-tert-butyl-4-hydroxy-5--methylbenzyl)-malonate,di-dodecylmercaptoethyl-2,2-bis-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate,bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.

1.9. Aromatic hydroxybenzyl compounds, for example1,3,5-tris-(3,5-di-tert-butyl--4-hydroxybenzyl)-2,4,6-trimethylbenzene,1,4-bis-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-trimethylbenzene,2,4,6-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.

1.10. Triazine Compounds, for example2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine,2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine,1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate,2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine,1,3,5-tris(3,5-tert-butyl-4-hydroxyphenylpropionyl-hexahydro-1,3,5-triazine,1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.

1.11. Benzylphosphonates, for exampledimethyl-2,5-di-tert-butyl-4-hydroxybenzyl-phosphonate,diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl-5-tert-butyl-4-hydroxy3-methylbenzylphosphonate, the calciumsalt of the monoethyl ester of3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid

1.12. Acylaminophenols, for example 4-hydroxylauranilide,4-hydroxystearanilide, octylN-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.

1.13. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid withmono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol,i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol, tris-(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol,3-thiapentadecanol trimethylhexaneiol, timethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.14. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acidwith mono- or polyhydric alcohols, e.g. with methanol, ethanol,n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethyleneglycol, diethylene glycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl) isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,timethylolopropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.15. Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid withmono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris-(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapnetadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.16. Esters of 3.5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono-or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris-(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.17. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid e.g.N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamine,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamine,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine.

1.18. Ascorbic acid (vitamin C)

1.19. Aminic antioxidants, for exampleN,N′-di-isopropyl-p-phenylenediamine, N,N′-di-sec-butyl-p-phenylenediamine,N,N′-bis(1,4-dimethylpentyl)-p-phenylenediamine,N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine,N,N′-bis(1-methylheptyl)-p-phenylenediamine,N,N′-dicyclohexyl-p-phenylenediamine, N,N′-diphenyl-p-phenylenediamine,N,N′-bis(2-naphthyl)-p-phenylenediamine,N-isopropyl-N′-phenyl-p-phenylenediamine,N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine,N-(1-methylheptyl)-N′-phenyl-p-phenylenediamine,N-cyclohexyl-N′-phenyl-p-phenylenediamine,4-(p-toluenesulfamoyl)diphenylamine,N,N′-dimethyl-N,N′-di-sec-butyl-p-phenylenediamine, diphenylamine,N-allyldiphenylamine, 4-isopropoxydiphenylamine,N-phenyl-1-naphthylamine, N-(4-tert--octylphenyl)-1-naphthylamine,N-phenyl-2-naphthylamine, octylated di-phenylamine, for examplep,p′-di-tert-octyldiphenylamine, 4-n-butylaminophenol,4-butyrylaminophenol, 4-nonanoylamino-phenol, 4-dodecanoylaminophenol,4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine,2,6-di-tert-butyl-4-dimethyl-aminoethylphenol,2,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane,N,N,N′,N′-tetramethyl-4,4′-diaminodiphenylmethane,1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino)propane,(o-tolyl)biguinide, Bis[4-(1′,3′-dimethylbutyl)phenyl]amine,tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- anddialkylated tert-butyl/tert-octyidiphenylamines, a mixture of mono- anddialkylated nonyldiphenylamines, a mixture of mono- and dialkylateddodecyidiphenylamines, a mixture of mono- and dialkylatedisopropyl/isohexyidiphenylamines, a mixture of mono-und dialkylatedtert-butyldiphenylamines,2,3-di-hydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, a mixtureof mono- und dialkylated tert-butyl/tert-octylphenothiazines, a mixtureof mono- und dialkylated tert-octyl-phenothiazines, N-allylphenothiazin,N,N, N′,N′-tetraphenyl-1,4-diamino-but-2-ene,N,N-bis(2,2,6,6-tetramethyl-piperid-4-yl-hexamethylenediamine,bis(2,2,6,6-tetramethylpiperid-4-yl)sebacate,2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol.

2. UV Absorbers and Light Stabilisers

Nickel compounds, for example nickel complexes of2,2′-thio-bis-[4-(1,1,3,3-tetra-methylbutyl)phenol], such as the 1:1 or1:2 complex, with or withou additional ligands such as n-butylamine,triethanolamine or N-cyclohexyldiethanolamine, nickeldibutyldithiocarbamate, nickel salts of the monoalkyl esters, e.g. themethyl or ethyl ester, of 4-hydroxy-3,5-di-tert-butylbenzylphosphonicacid, nickel complexes of ketoximes, e.g. of 2-hydroxy-4-methylphenylundecylketoxime, nickel complexes of1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additionalligands.

3. Metal deactivators, for example N,N′-diphenyloxamide,N-salicylal-N′-salicyloyl hydrazine, N, N′-bis(salicyloyl) hydrazine,N,N′-bis(3,5-di-tert-butyl-4-hydroxy-phenylpropionyl) hydrazine ,3-salicyloylamino-1,2,4-triazole, bis(benzylidene)-oxalyl dihydrazide,oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenyl-hydrazide,N,N′-diacetyladipoyl dihydrazide, N,N′-bis(salicyloyl)oxalyldihydrazide, N,N′-bis(salicyloyl)thiopropionyl dihydrazide.

4. Phosphites and phosphonites, for example triphenyl phosphite,diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite,diisodecyl pentaerythritol, diphosphite, tris(2,4-di-tert-butylphenyl)phosphite, diisodecyl pentaerythritol diphoshite,bis(2,4-di-tert-butylphenyl)-pentaerythritol diphoshite,diisodecyloxypentaerythritol diphosphite,bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite,tristearyl sorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)4,4′-biphenylene diphosphonite,6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-1,3,2-dioxaphosphocin,bis(2,4-di-tert-butyl-6-methyl-phenyl)methylphosphite,bis(2,4-di-tert-butyl-6-methylphenyl)ethylphosphite.

5. Hydroxylamines, for example, N,N-dibenzylhydroxylamine,N,N-diethylhydroxyl-amine, N,N-dioctylhydroxylamine,N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine,N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine,N-hexadecyl-N-octadecylhydroxylamine,N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derivedfrom hydrogenated tallow amine.

6. Nitrones, for example, N-benzyl-alpha-phenyl-nitrone,N-ethyl-alpha-methyl-nitrone, N-octyl-alpha-heptyl-nitrone,N-lauryl-alpha-undecyl-nitrone, N-tetradecyl-alpha-tridecyl-nitrone,N-hexadecyl-alpha-pentadecyl-nitrone,N-octadecyl-alpha-heptadecyl-nitrone,N-hexadecyl-alpha-heptadecyl-nitrone,N-octadecyl-alpha-pentadecyl-nitrone,N-heptadecyl-alpha-heptadecyl-nitrone,N-octadecyl-alpha-hexadecyl-nitrone, nitrone derived fromN,N-dialkylhydroxylamine derived from hydrogenated tallow amine.

7. Thiosynergists, for example, dilauryl thiodipropionate or distearylthiodipropionate.

8. Peroxide scavengers, for example esters of β-thiodipropionic acid,for example the lauryl, stearyl, myristyl or tridecyl esters,mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zincdibutyidithiocarbamate, dioctadecyl disulfide, pentaerythritoltetrakis(p-dodecylmercapto)propionate.

9. Basic co-stabilisers, for example, melamine, polyvinylpyrrolidone,dicyandiamide, triallyl cyanurate, urea derivatives, hydrazinederivatives, amines, polyamides, polyurethanes, alkali metal salts andalkaline earth metal salts of higher fatty acids for example calciumstearate, zinc stearate, magnesium behenate, magnesium stearate, sodiumricinoleate and potassium palmitate, antimony pyrocatecholate or tinpyrocatecholate.

10. Nucleating agents, for example, inorganic substances such as talcum,metal oxides such as titanium dioxide or magnesium oxide, phosphates,carbonates or sulfates of, preferably, alkaline earth metals; organiccompounds such as mono- or polycarboxylic acids and the salts thereof,e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodiumsuccinate or sodium benzoate; polymeric compounds such as ioniccopolymers (“ionomers”).

11. Fillers and reinforcing agents, for example, calcium carbonate,silicates, glass fibres, glass bulbs, asbestos, talc, kaolin, mica,barium sulfate, metal oxides and hydroxides, carbon black, graphite,wood flour and flours or fibers of other natural products, syntheticfibers.

12. Other additives, for example, plasticisers, lubricants, emulsifiers,pigments, rheology additives, catalysts, flow-control agents, opticalbrighteners, flameproofing agents, antistatic agents and blowing agents.

13. Benzofuranones and indolinones, for example those disclosed in U.S.Pat. Nos. 4,325,863, 4,338,244, 5,175,312, 5,216,052, 5,252,643,DE-A-4316611, DE-A-4316622, DE-A-4316876, EP-A-0589839 or EP-A-0591102or 3--[4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butyl-benzofuran-2-one,5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one,3,3′-bis[5,7-di-tert-butyl-3-(4-[2--hydroxyethoxy]phenyl)benzofuran-2-one],5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one,3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2--one,3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl-benzofuran-2-one.

The weight ratio of the total amount of components (I), (II) andoptionally (X-1) and/or (X-2), as well as optionally component (XX) tothe total amount of the conventional additives can be, for example,100:1 to 1:100.

The examples below illustrate the invention in greater detail. Allpercentages and parts are by weight, unless stated otherwise.

Stabilizers Used in the Following Examples I to IV:

(For the polymeric compounds, the mean degree of polymerization isindicated in each case.)

Compound (B-1-a-1):

(CHIMASSORB 944 (RTM))

with b₁ being 4.5.

Compound (B-2-a-1):

(CHIMASSORB 119 (RTM))

Compound (B-7-a-1):

(TINUVIN 622 (RTM))

with n₁ being 5.1.

Compound (X-2-a):

TINUVIN 327 (RTM)

Example I

Light Stabilization of Polypropylene Tapes.

100 parts of polypropylene powder (melt flow index: 3.2 g/l0 min at 230°C. and 2160 g) are blended in a barrel mixer with 0.05 parts ofpentaerythrityltetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 0.005 partsof tris[2,4-di-tert-butylphenyl]phosphite and the stabilizer systemindicated in Table 1. Then, the blend is compounded in an extruder attemperatures of 180°-220° C. The granules obtained on extrusion andgranulation are transformed into films at 220°-260° C. in a secondextruder equipped with a flat sheet die. The films are cut into ribbonswhich are drawn to achieve a stretch ratio of 1:6. The tapes obtainedwith this procedure are finally 50 Em thick and 2.5 mm wide.

The tapes are mounted without tension on sample holders and exposed tonatural weathering in Florida (450 South, direct, approximately 145kLy/year). Periodically, the tensile strength of the exposed tapes ismeasured. The received energy (in kLy) corresponding to a loss of 50%(E₅₀) of the initial tensile strength or the % retained tensile strengthafter 320 kLy is a measure for the stabilizing efficiency of thestabilizer system.

The values obtained are summarized in Table 1.

TABLE 1 E₅₀ (kLy) to 50% retained tensile strength or Stabilizer System% retained tensile strength after 320 kLy 0.1% of Mg stearate 58   0.05% of (B-1-a-1) + 78% 0.05% of (B-7-a-1) + 0.1% of Mg stearate

Example II

Light Stabilization of Polypropylene Homopolymer Films.

100 parts of unstabilized polypropylene powder (melt flow index: 3.8 g/l0 min at 230° C. and 2160 g) are homogenized at 200° C. for 10 min in aBrabender plastograph with 0.05 parts ofpentaerythrityl-tetrakis{3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate},0.10 parts of tris{2,4-di-tert-butylphenyl}phosphite and the stabilizersystem indicated in Tables 2a, 2b, 2c and 2d. The material thus obtainedis compression molded in a laboratory press between two aluminum foilsfor 6 min at 260° C. to a 0.5 mm thick film which is cooled immediatelyto room temperature in a water-cooled press. Samples of 60 mm×25 mm arecut out of these 0.5 mm films and are exposed in a WEATHER-OMETER Ci 65(black panel temperature 63±2° C., without water-spraying).

Periodically, these samples are removed from the exposure apparatus andtheir carbonyl content is measured with an infrared spectrophotometer.The exposure time corresponding to formation of a carbonyl absorbance of0.1 in hours (T_(0.1)) is a measure for the efficiency of the stabilizersystem. The values obtained are summarized in Tables 2a, 2b, 2c and 2d.

TABLE 2a T_(0.1) in hours to 0.1 Stabilizer system carbonyl absorbance0.1% of Mg stearate + 0.1% of (X-2-a)  360 0.025% of (B-1-a-1) + 0.025%of (B-7-a-1) + 1960 0.1% of Mg stearate + 0.1% of (X-2-a) 0.025% of(B-2-a-1) + 0.025% of (B-7-a-1) + 1820 0.1% of Mg stearate + 0.1% of(X-2-a)

TABLE 2b T_(0.1) in hours to 0.1 Stabilizer system carbonyl absorbance0.1% of Zn stearate + 0.5% of TiO₂ (rutile)  430 0.025% of (B-1-a-1) +0.025% of (B-7-a-1) + 1540 0.1% of Zn stearate + 0.5% of TiO₂ (rutile)0.025% of (B-2-a-1) + 0.025% of (B-7-a-1) + 1840 0.1% of Zn stearate +0.5% of TiO₂ (rutile)

TABLE 2c T_(0.1) in hours to 0.1 Stabilizer system carbonyl absorbance0.025% of (B-1-a-1) + 0.025% of (B-7-a-1) + 2020 0.1% of hydrotalcite(DHT-4A (RTM)) + 0.5% of TiO₂ (rutile)

TABLE 2d T_(0.1) in hours to 0.1 Stabilizer system carbonyl absorbance0.025% of (B-1-a-1) + 0.025% of (B-7-a-1) + 2320 0.1% of hydrotalcite(DHT-4A (RTM)) + 0.1% of (X-2-a)

Example III

Light Stabilization of Polypropylene Copolymer Films.

100 parts of unstabilized copolypropylene powder (melt flow index: 6g/10 min at 230° C. and 2160 g; 10% ethylene monomer) are homogenized at200° C. for 10 min in a Brabender plastograph with 0.05 parts ofpentaerythrityl-tetrakis{3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate},0.10 parts of tris{2,4-di-tert-butylphenyl} phosphite and the stabilizersystem indicated in Table 3. The material thus obtained is compressionmolded in a laboratory press between two aluminum foils for 6 min at260° C. to a 0.5 mm thick film which is cooled immediately to roomtemperature in a water-cooled press. Samples of 60 mm×25 mm are cut outof these 0.5 mm films and are exposed in a WEATHER-OMETER Ci 65 (blackpanel temperature 63±2° C., without water-spraying).

Periodically, these samples are removed from the exposure apparatus andtheir carbonyl content is measured with an infrared spectrophotometer.The exposure time corresponding to formation of a carbonyl absorbance of0.1 is a measure for the efficiency of the stabilizer system. The valuesobtained are summarized in Table 3.

TABLE 3 T_(0.1) in hours to 0.1 Stabilizer system carbonyl absorbance0.1% of hydrotalcite (DHT-4A (RTM)) +  390 0.5% of TiO₂ (rutile) 0.05%of (B-1-a-1) + 0.05% of (B-7-a-1) + 4000 0.1% of hydrotalcite (DHT-4A(RTM)) + 0.5% of TiO₂ (rutile) 0.05% of (B-2-a-1) + 0.05% of (B-7-a-1) +4960 0.1% of hydrotalcite (DHT-4A (RTM)) + 0.5% of TiO₂ (rutile)

Example IV

Light Stabilization of Polyethylene HD Films.

100 parts of unstabilized high density polyethylene powder (density:0.964 g cm⁻³, melt flow index: 5.0 g/10 min at 190° C. and 2160 g) arehomogenized at 180° C. for 10 min in a Brabender plastograph with 0.03parts of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate andthe stabilizer system indicated in Tables 4a, 4b, 4c, 4d, 4e, 4f, 4g, 4hand 4i.

The material thus obtained is compression molded in a laboratory pressbetween two aluminum foils for 6 min at 210° C. to a 0.5 mm thick filmwhich is cooled immediately to room temperature in a water-cooled press.Samples of 60 mm×25 mm are cut out of these 0.5 mm films and are exposedin a WEATHER-OMETER Ci 65 (black panel temperature 63±2° C., withoutwater-spraying).

Periodically, these samples are removed from the exposure apparatus andtheir carbonyl content is measured with an infrared spectrophotometer.The exposure time corresponding to formation of a carbonyl absorbance of0.1 is a measure for the efficiency of the stabilizer mixture. Thevalues obtained are summarized in Table 4a, 4b, 4c, 4d, 4e, 4f, 4g, 4hand 4i.

TABLE 4a T_(0.1) in hours to 0.1 Stabilizer system carbonyl absorbance0.025% of (B-1-a-1) + 0.025% of (B-7-a-1) + 18060 0.1% of Mg stearate

TABLE 4b T_(0.1) in hours to 0.1 Stabilizer system carbonyl absorbance0.025% of (B-1-a-1) + 0.025% of (B-7-a-1) + 18055 0.1% of hydrotalcite(DHT-4A (RTM))

TABLE 4c T_(0.1) in hours to 0.1 Stabilizer system carbonyl absorbance0.025% of (B-1-a-1) + 0.025% of (B-7-a-1) + 22210 0.05% of Mg stearate +0.05% of Ca stearate

TABLE 4d T_(0.1) in hours to 0.1 Stabilizer system carbonyl absorbance0.025% of (B-1-a-1) + 0.025% of (B-7-a-1) + 15680 0.05% of hydrotalcite(DHT-4A (RTM)) + 0.1% of Ca stearate

TABLE 4e T_(0.1) in hours to 0.1 Stabilizer system carbonyl absorbance0.025% of (B-1-a-1) + 0.025% of (B-7-a-1) + 23040 0.05% of hydrotalcite(DHT-4A (RTM)) + 0.1% of Mg stearate

TABLE 4f T_(0.1) in hours to 0.1 Stabilizer system carbonyl absorbance0.025% of (B-1-a-1) + 0.025% of (B-7-a-1) + >28700 0.1% of Mg stearate +0.5% of TiO₂ (rutile)

TABLE 4g T_(0.1) in hours to 0.1 Stabilizer system carbonyl absorbance0.025% of (B-1-a-1) + 0.025% of (B-7-a-1) + >28700 0.05% of Mgstearate + 0.5% of TiO₂ (rutile) + 0.05% of Ca stearate

TABLE 4h T_(0.1) in hours to 0.1 Stabilizer system carbonyl absorbance0.025% of (B-1-a-1) + 0.025% of (B-7-a-1) + >28700 0.05% of hydrotalcite(DHT-4A (RTM)) + 0.5% of TiO₂ (rutile) + 0.05% of Ca stearate

TABLE 4i T_(0.1) in hours to 0.1 Stabilizer system carbonyl absorbance0.025% of (B-1-a-1) + 0.025% of (B-7-a-1) + >28700 0.05% of hydrotalcite(DHT-4A (RTM)) + 0.5% of TiO₂ (rutile) + 0.05% of Mg stearate

What is claimed is:
 1. A stabilizer mixture containing (I) two differentsterically hindered amine compounds selected from the group consistingof the classes, (β-1) a compound of the formula (B-1):

in which R₁, R₃, R₄ and R₅ independently of one another are hydrogen,C₁-C₁₂alkyl, C₅-C₁₂cycloalkyl, C₁-C₄-alkyl-substituted C₅-C₁₂cycloalkyl,phenyl, phenyl which is substituted by —OH and/or C₁-C₁₀alkyl;C₇-C₉phenylalkyl, C₇-C₉phenylalkyl which is substituted on the phenylradical by —OH and/or C₁-C₁₀alkyl; or a group of the formula (b-I):

R₂ is C₂-C₁₈alkylene, C₅-C₇cycloalkylene orC₁-C₄alkylenedi(B5-C₇cycloalkylene), or the radicals R₁, R₂ and R₃,together with the nitrogen atoms to which they are bonded, perform a 5-to 10-membered heterocyclic ring, or R₄ and R₅, together with thenitrogen atom to which they are bonded, form a 5- to 10-memberedheterocyclic ring, R₆ is hydrogen, C₁-C₈alkyl, O, —OH, —CH₂CN,C₁-C₁₈alkoxy, C₅-C₁₂cycloalkoxy, C₃-C₆alkenyl, C₇-C₉phenylalkylunsubstituted or substituted on the phenyl by 1, 2 or 3 C₁-C₄alkyl; orC₁-C₈acyl, and b₁ is a number from 2 to 50, with the proviso that atleast one of the radicals R₁, R₃, R₄ and R₅ is a group of the formula(b-I): (β-2) a compound of the formula (B-2):

wherein R₇ and R₁₁ independently of one another are hydrogen orC₁-C₁₂alkyl, R₈, R₉ and R₁₀ independently of one another areC₂-C₁₀alkylene, and X₁, X₂, X₃, X₄, X₅, X₆, X₇ and X₈ independently ofone another are a group of the formula (b-II):

in which R₁₂ is hydrogen, C₁-C₁₂alkyl, C₅-C₁₂cycloalkyl,C₁-C₄alkyl-substituted C₅-C₁₂cycloalkyl, phenyl, —OH— and/orC₁-C₁₀alkyl-substituted phenyl, C₇-C₉phenylalkyl, C₇-C₉phenylalkyl whichis substituted on the phenyl radical by —OH and/or C₁-C₁₀alkyl; or agroup of the formula (b-I) as defined above, and R₁₃ has one of themeanings of R₆; (β-6) a product (B-6) obtainable by reacting a product,obtained by reaction of a polyamine of the formula (B-6-1) with cyanuricchloride, with a compound of the formula (B-6-2): H₂—(CH₂)_(b) ₅_(′)—NH—(CH₂)_(b) ₅ _(″)—NH—(CH₂)_(b) ₅ _(′″)—NH₂  (B-6-1))

in which b₅′, b₅″ and b₅′″ independently of one another are a numberfrom 2 to 12, R₃₁ is hydrogen, C₁-C₁₂alkyl, C₅-C₁₂cycloalkyl, phenyl orC₇-C₉phenylalkyl, and R₃₂ has one of the meanings of R₆; (β-7) acompound of the formula (B-7):

wherein A₁ is hydrogen or C₁-C₄alkyl, A₂ is a direct bond orC₁-C₁₀alkylene, and n₁ is a number from 2 to 50; and (β-8) at least onecompound of the formulae (B-8-a) or (B-8-b):

wherein n₂ and n₂* are a number from 2 to 50; and (II) at least onecompound selected from the group consisting of an organic salt of Zn, aninorganic salt of Zn, Zn oxide, Zn hydroxide, an organic salt of Mg, aninorganic salt of Mg, Mg oxide and Mg hydroxide; with the proviso thatcomponent (I) is different from the combination of the compounds (B-8-a)and (B-8-b):

wherein n₂ and n₂* are a number from 2 to 50; and with the proviso that,when component (I) is the combination of the compounds (B-1-a-1) and(B-7-a):

wherein b₁ is a number from 2 to 50,

wherein n₁ is a number from 2 to 50; and, at the same time, component(II) is a Zn carboxylate; the stabilizer mixture additionally containsas a further component (X-1) a pigment or (X-2) an UV absorber or (X-3)a pigment and an UV absorber.
 2. A stabilizer mixture according to claim1, wherein the product (B-6) is represented by a compound of the formula(B-6-α), (B-6-β) or (B-6-γ), or a mixture thereof:

wherein R₃₁ and R₃₂ are as defined in claim 1 and b₅ is a number from 2to
 20. 3. A stabilizer mixture according to claim 1 wherein the class(β-6) relates to a compound of the formula:

with b₅ being a number from 2 to
 20. 4. A stabilizer mixture accordingto claim 1, wherein one of the two different sterically hindered aminecompounds of component (I) is selected from the class (β-1).
 5. Astabilizer mixture according to claim 1, wherein one of the twodifferent sterically hindered amine compounds of component (I) isselected from the class (β-1), and the other of the two differentsterically hindered amine compounds of component (I) is selected fromthe class (β-7).
 6. A stabilizer mixture according to claim 1, whereinone of the two different sterically hindered amine compounds ofcomponent (I) is selected from the class (β-7), and the other of the twodifferent sterically hindered amine compounds of component (I) isselected from the class (β-2).
 7. A stabilizer mixture according toclaim 1, wherein the two different sterically hindered amine compoundsof component (I) are selected from different classes.
 8. A stabilizermixture according to claim 1, wherein: R₁ and R₃ independently of oneanother are a group of the formula (b-I), R₂ is C₂-C₈alkylene, R₄ and R₅independently of one another are hydrogen, C₁-C₁₂alkyl, C₅-C₈cycloalkylor a group of the formula (b-I), or the radicals R₄ and R₅, togetherwith the nitrogen atom to which they are bonded, form a 5- to10-membered heterocyclic ring, and b₁ is a number from 2 to 25; R₇ andR₁₁ independently of one another are hydrogen or C₁-C_(4alkyl,) R₈, R₉and R₁₀ independently of one another are C₂-C₄alkylene, and X₁, X₂, X₃,X₄, X₅, X₆, X₇ and X₈ independently of one another are a group of theformula (b-II), R₁₂ is hydrogen, C₁-C₄alkyl, C₅-C₈cycloalkyl or a groupof the formula (b-I); b₅′, b₅″ and b₅′″ independently of one another area number from 2 to 4, and R₃₁ is hydrogen, C₁-C₄alkyl, C₅-C₈cycloalkyl,phenyl or benzyl; A₁ is hydrogen or methyl, A₂ is a direct bond orC₂-C₆alkylene, and n₁ is a number from 2 to 25; n₂ and n₂* are a numberfrom 2 to
 25. 9. A stabilizer mixture according to claim 1, wherein thetwo different sterically hindered amine compounds of component (I) areselected from the group consisting of the compounds of the formulae(B-1-a), (B-1-b), (B-1-c), (B-1-d) and (B-2-a), a product (B-6-a) andthe compounds of the formulae (B-7-a), (B-8-a) and (B-8-b):

wherein b₁ is a number from 2 to 20 and R₆ is hydrogen, C₁-C₈alkyl, O,—OH, —CH₂CN, C₁-C₁₈alkoxy, C₅-C₁₂cycloalkoxy, C₃-C₆alkenyl,C₇-C₉phenylalkyl unsubstituted or substituted on the phenyl by 1, 2 or 3C₁-C₄alkyl; or C₁-C₈acyl;

wherein R₁₃ has one of the meanings of R₆, a product (B-6-a) obtainableby reacting a product, obtained by reaction of a polyamine of theformula (B-6-1-a) with cyanuric chloride, with a compound of the formula(B-6-2-a):

in which R₃₂ has one of the meanings of R₆;

wherein n₁ is a number from 2 to 20

wherein n₂ and n₂* are a number from 2 to
 20. 10. A stabilizer mixtureaccording to claim 9 wherein the two different sterically hindered aminecompounds of component (I) are 1) a compound of the formula (B-1-a)wherein R₆ is hydrogen, and a compound of the formula (B-7-a); or 2) acompound of the formula (B-2-a) wherein R₁₃ is methyl, and a compound ofthe formula (B-7-a).
 11. A stabilizer mixture according to claim 1wherein R₆, R₁₃ and R₃₂ are hydrogen, C₁-C₄alkyl, C₁-C₁₀alkoxy,cyclohexyloxy, allyl, benzyl or acetyl.
 12. A stabilizer mixtureaccording to claim 9 wherein R₆, R₁₃ and R₃₂ are hydrogen or methyl andR₆ additionally is C₁-C₈alkoxy.
 13. A stabilizer mixture according toclaim 1, wherein the compound of component (II) is selected from thegroup consisting of Mg carboxylates, Zn carboxylates, Mg oxides, Znoxides, Mg hydroxides, Zn hydroxides, Mg carbonates and Zn carbonates.14. A stabilizer mixture according to claim 1, which additionallycontains as a further component (X-1) a pigment or (X-2) an UV absorberor (X-3) a pigment and an UV absorber.
 15. A stabilizer mixtureaccording to claim 1, which additionally contains as a further component(XX) an organic salt of Ca, an inorganic salt of Ca, Ca oxide or Cahydroxide.
 16. A composition comprising an organic material subject todegradation induced by light, heat or oxidation and a stabilizer mixtureaccording to claim
 1. 17. A composition according to claim 16 whereinthe organic material is a synthetic polymer.
 18. A composition accordingto claim 16 wherein the organic material is a polyolefin.
 19. Acomposition according to claim 16 wherein the organic material ispolyethylene, polypropylene, a polyethylene copolymer or a polypropylenecopolymer.
 20. Polypropylene containing a compound of the formula (B-1),a compound of the formula (B-7) and a Zn-carboxylate:

in which R₁, R₃, R₄ and R₅ independently of one another are hydrogen,C₁-C₁₂alkyl, C₅-C₁₂cycloalkyl, C₁-C₄-alkyl-substituted C₅-C₁₂cycloalkyl,phenyl, phenyl which is substituted by —OH and/or C₁-C₁₀alkyl;C₇-C₉phenylalkyl, C₇-C₉phenylalkyl which is substituted on the phenylradical by —OH and/or C₁-C₁₀alkyl; or a group of the formula (b-I):

R₂ is C₂-C₁₈alkylene, C₅-C₇cycloalkylene orC₁-C₄alkylenedi(B₅—C₇cycloalkylene), or the radicals R₁, R₂ and R₃,together with the nitrogen atoms to which they are bonded, perform a 5-to 10-membered heterocyclic ring, or R₄ and R₅, together with thenitrogen atom to which they are bonded, form a 5- to 10-memberedheterocyclic ring, R₆ is hydrogen, C₁-C₈alkyl, O, —OH, —CH₂CN,C₁-C₁₈alkoxy, C₅-C₁₂cycloalkoxy, C₃-C₆alkenyl, C₇-C₉phenylalkylunsubstituted or substituted on the phenyl by 1, 2 or 3 C₁-C₄alkyl; orC₁-C₈acyl, and b₁ is a number from 2 to 50, with the proviso that atleast one of the radicals R₁, R₃, R₄ and R₅ is a group of the formula(b-I):

wherein A₁ is hydrogen or C₁-C₄alkyl, A₂ is a direct bond orC₁-C₁₀alkylene, and n₁ is a number from 2 to
 50. 21. A method forstabilizing an organic material against degradation induced by light,heat or oxidation, which comprises incorporating into the organicmaterial a stabilizer mixture according to claim 1.